JP6600972B2 - Oligofluorene epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Description

  The present invention relates to a novel oligofluorene epoxy resin, a method for producing the same, a resin composition containing the novel oligofluorene epoxy resin, and a cured product thereof.

Cured products obtained by curing epoxy resin compositions (hereinafter sometimes referred to as resin cured products) are paints, inks, coating agents, adhesives, adhesives, sealing materials, insulating materials, electronic materials, holo It is used in a wide range of industrial applications such as graphic memory, optical materials, laminates, and resists, and its required performance has become increasingly sophisticated in recent years.
As an epoxy resin in which the cured product satisfies high transparency and refractive index, a diepoxy compound in which fluorene is crosslinked with an alkylene group having 2 to 10 carbon atoms has been proposed (see Patent Document 1).

  The difluorange epoxy resin crosslinked with a pentylene group specifically disclosed in Patent Document 1 is a viscous liquid, and the difluorange epoxy resin crosslinked with a hexylene group is described as a white crystal. Further, it is described that a cured product of a difluorange epoxy resin crosslinked with a pentylene group is excellent in transparency after a short heating test.

JP 2013-193958 A

  However, Patent Document 1 specifically discloses only a difluor orange epoxy resin crosslinked with a pentylene group or a hexylene group, and the refractive index of the cured product obtained from the epoxy resin is also the refractive index of the cured product. The refractive index of the epoxy resin itself that affects the value of the rate is not evaluated at all. Generally, it is known that the refractive index decreases as the proportion of saturated hydrocarbons increases, and it is unclear whether the epoxy resin specifically disclosed in Patent Document 1 has a sufficiently high refractive index.

  Since the refractive index is considered to be increased when the cross-linking group of fluorene is shorter, the inventors synthesized and evaluated a difluor orange epoxy resin cross-linked with an ethylene group having 2 carbon atoms. Was found to be a high melting crystalline compound with a temperature of 228 ° C. Thus, since the difluor orange epoxy resin whose crosslinking group is an ethylene group has a high melting point, it has been found that it is difficult to use it under normal epoxy curing conditions in which it is melted at a low temperature and cured at a high temperature.

  An object of the present invention is to provide an epoxy resin that has a low melting point, good processability, high refraction, and is suitably used for optical applications. It is another object of the present invention to provide an oligofluorene compound that is a raw material for producing the epoxy resin.

As a result of intensive studies to solve the above problems, the present inventors have found that a specific oligofluorene epoxy resin has a sufficiently high refractive index, a low melting point, and excellent workability. The headline, the present invention has been reached.
That is, the gist of the present invention is as follows.
[1] An oligo comprising two or more fluorene units which may have a substituent, wherein the 9-position carbon atoms of the fluorene units are linked in a chain form via a methylene group Fluorene epoxy resin.
[2] The oligofluorene epoxy resin according to [1], which is represented by the following general formula (1).

(Wherein R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted group) An optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10 acyloxy groups, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.

R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. )
[3] The oligofluorene epoxy resin according to [2], wherein R ¹ and R ² are methylene groups.
[4] Oligofluorene epoxy resin represented by general formula (1) according to [2] or [3] by oxidizing oligofluorene having a carbon-carbon double bond represented by the following general formula (2) A process for producing an oligofluorene epoxy resin, characterized in that

(Wherein R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted group) An optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10 acyloxy groups, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.

R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. )
[5] An oligofluorene epoxy resin composition comprising the oligofluorene epoxy resin according to any one of [1] to [3].
[6] An oligofluorene compound having a carbon-carbon double bond, which is represented by the following general formula (2).

(Wherein R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted group) An optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10 acyloxy groups, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.

R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. )
[7] An epoxy (meth) acrylate compound represented by the following general formula (5).

(Wherein R ¹ , R ² , R ^{4 to} R ¹⁰ have the same meanings as in the general formula (1).
R ¹² is a hydrogen atom or a methyl group,
R ¹³ represents a hydrogen atom or an acyl group.
n shows the integer value of 1-5. )
[8] A composition comprising the oligofluorene compound having a carbon-carbon double bond according to [6] or the epoxy (meth) acrylate compound according to [7].
[9] A cured product obtained by curing the oligofluorene epoxy resin composition according to [5] or the composition according to [8].
[10] The cured product according to [9], wherein the halogen atom content is 1000 mass ppm or less.
[11] An optical material comprising the cured product according to [9] or [10].
[12] An electronic material comprising the cured product according to [9] or [10].

  The oligofluorene epoxy resin of the present invention has a sufficiently high refractive index, a low melting point, and excellent workability.

DESCRIPTION OF EMBODIMENTS Embodiments of the present invention will be described in detail below. However, the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention. It is not limited to the contents. In the present invention, “weight” is synonymous with “mass”.
In the present invention, “optionally substituted” is synonymous with “optionally substituted”.

<1 Oligofluorene epoxy resin>
The oligofluorene epoxy resin of the present invention contains two or more fluorene units which may have a substituent.
In the oligofluorene epoxy resin, the 9-position carbon atoms of the fluorene unit are bonded in a chain via a methylene group.

  As described above, the oligofluorene epoxy resin of the present invention has fluorene units bonded in a chain form through a methylene group having a short carbon number, so the ratio of fluorene units per molecule is high, and a high refractive index is expressed. ing. Nevertheless, the epoxy resin in which the fluorene unit is cross-linked with a long-chain alkylene group in order to form a unique structure by combining the fluorene ring with a chain structure via a methylene group. Unlikely, it is considered that the melting point is specifically low.

<1.1 Substituent which fluorene unit may have>
In the oligofluorene epoxy resin of the present invention, examples of the substituent that the fluorene unit may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms. (Eg, methyl group, ethyl group, isopropyl group, etc.); C 1-10 alkoxy group (eg, methoxy group, ethoxy group, etc.); C 1-10 acyl group (eg, acetyl group, benzoyl group, etc.) C1-10 acylamino group (eg, acetamide group, benzoylamide group, etc.); C1-10 acyloxy group (eg, acetoxy group, benzoyloxy group, etc.); nitro group; cyano group; halogen atom (Eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), carbon 1-10 alkoxy groups (eg, methoxy group, ethoxy group, etc.), C1-C10 acyl groups (eg, acetyl group, benzoyl group, etc.), C1-C10 acylamino groups (eg, acetamido group, A benzoylamide group, etc.), a nitro group, a cyano group and the like, and an aryl group having 4 to 10 carbon atoms (eg, phenyl group, naphthyl group, etc.) optionally having 1 to 3 substituents. It is done. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

<1.2 Epoxy group>
In the oligofluorene epoxy resin of the present invention, among the two or more fluorene units, substituents α ¹ and α ² are bonded to the 9th carbon atom of the fluorene unit located at both ends, respectively, and the substituent α ¹ and The α ² may have an epoxy group bonded thereto. In this case, α ¹ and α ² may be the same or different. Further, the substituents α ¹ and α ² include a direct bond, that is, an epoxy group may be directly bonded to the 9th-position carbon atom of the fluorene unit.

Although it does not specifically limit as an epoxy group which the oligo fluorene epoxy resin of this invention has, You may have a C1-C10 alkyl group which may be substituted as a substituent.
Specific examples of the alkyl group having 1 to 10 carbon atoms include, but are not limited to, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n- Linear alkyl groups such as hexyl group and n-decyl group; branched alkyl groups such as isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 2-ethylhexyl group; cyclopropyl group, Examples thereof include cyclic alkyl groups such as cyclopentyl group, cyclohexyl group, and cyclooctyl group.

The substitution site of the optionally substituted alkyl group having 1 to 10 carbon atoms is not particularly limited, but from the viewpoint of easy introduction of the substituent, in the epoxy group, in the carbon atom to which the substituents α ¹ and α ² are bonded. It is preferred to replace the bonded hydrogen atom.
Among these, an unsubstituted or alkyl group having 1 to 6 carbon atoms is preferable from the viewpoint of being industrially available at a low cost. Furthermore, if there is a sterically bulky substituent, the reactivity of the epoxy group may be lowered, and therefore unsubstituted or methyl groups are particularly preferred.

<1.3 Substituents α ¹ and α ² >
The substituents α ¹ and α ² are not particularly limited, but may be a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted group. An optionally substituted aralkylene group having 5 to 12 carbon atoms, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and optionally substituted. A group in which two or more groups selected from the group consisting of aralkylene groups having 5 to 12 carbon atoms are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group; Can be mentioned.

The “optionally substituted alkylene group having 1 to 10 carbon atoms” is preferably one having 4 or more carbon atoms from the viewpoint of lowering the melting point and improving processability. On the other hand, from the viewpoint of improving the glass transition temperature, the carbon number is preferably 3 or less, more preferably 2 or less, and even more preferably 1. Further, when the number of carbon atoms is 1, it is particularly preferable from the viewpoint that it can be produced using raw materials that are industrially inexpensive and easily available.

  Specific examples of the alkylene group include, but are not limited to, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-pentylene group, and an n-hexylene group. A linear alkylene group: methylmethylene group, dimethylmethylene group, ethylmethylene group, propylmethylene group, butylmethylene group, (1-methylethyl) methylene group, 1-methylethylene group, 2-methylethylene group, 1 -Includes branched chains such as ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2,2-dimethylpropylene group, 3-methylpropylene group An alkylene group (the value of the substitution position is attached from the carbon on the fluorene ring side); a fat as shown in the following group [A] Any cycloaliphatic alkylene group having a linear or a bond of branched alkylene group in two places structure

(The position of substitution of two bonds in each ring structure shown in the group [A] is arbitrary, and two bonds may be substituted on the same carbon.); A heterocyclic alkylene group having a bond of a linear or branched alkylene group at any two positions of the heterocyclic structure

(The position of substitution of two bonds in each ring structure shown in the above [B] group is arbitrary, and two bonds may be substituted on the same carbon).
Bonding of a linear or branched alkylene group at any two positions of the alicyclic structure as shown in the group [A] or the heterocyclic structure as shown in the group [B]. Specific examples of the structure of the hand include the following, but are not limited thereto, but include straight chain such as methylene group, ethylene group, n-propylene group, n-butylene group, n-pentylene group, and n-hexylene. 1-methylethylene group, 2-methylethylene group, 1-ethylethylene group, 2-ethylethylene group, 1-methylpropylene group, 2-methylpropylene group, 1,1-dimethylethylene group, 2 , 2-dimethylpropylene group, alkylene group containing a branched chain such as 3-methylpropylene group (here, the numerical value of the substitution position is attached from carbon bonded to the ring structure).

Examples of the substituent that the alkylene group may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.) C1-10 acyl group (eg, acetyl group, benzoyl group, etc.); C1-10 acylamino group (eg, acetamido group, benzoylamide group, etc.); nitro group; cyano group; oxo group; Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), alkoxy group having 1 to 10 carbon atoms (eg, , Methoxy group, ethoxy group, etc.), C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.), C1-C10 acylamino group (eg, acetamido group, benzoylamino) Group), a nitro group, an aryl group (e.g. 1 to 3 substituents which may 4-10 carbon atoms which may have a selected from a cyano group, a phenyl group, a naphthyl group, etc.) and the like. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

  Specific examples of the alkylene group which may be substituted include an alkyl group-substituted alkylene group such as a cyclobutylmethylene group, a cyclopentylmethylene group, a cyclohexylmethylene group, and a 1-cyclohexylpropylene group; a phenylmethylene group, a 1-phenylethylene group, Aryl group-substituted alkylene groups such as 1-phenylpropylene group; oxoalkylene groups such as oxomethylene group, 1-oxopropylene group and 3-oxopropylene group; 1,1,2,2-tetrafluoroethylene group, trichloromethylmethylene Group, halogen atom-substituted alkylene group such as trifluoromethylmethylene group; alkoxy group-substituted alkylene group such as 2-methoxymethyl-2-methylpropylene group, etc. (the numerical value of the substitution position is attached from the carbon on the fluorene ring side) Suppose ).

The “optionally substituted arylene group having 4 to 10 carbon atoms” usually has 4 or more carbon atoms, usually 10 or less, preferably 8 or less, more preferably 6 or less. is there.
Specific examples of the arylene group include, but are not limited to, phenylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group; Naphthylene groups such as 2,5-naphthylene group and 2,6-naphthylene group; and heteroarylene groups such as 2,5-pyridylene group, 2,4-thienylene group and 2,4-furylene group.

  Examples of the substituent that the arylene group may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, Isopropyl group, etc.); C1-C10 alkoxy group (eg, methoxy group, ethoxy group, etc.); C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.); C1-C10 acylamino Groups (eg, acetamido group, benzoylamide group, etc.); nitro groups; cyano groups, and the like. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

  Specific examples of the arylene group which may be substituted include 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, 3,5-dimethyl-1,4-phenylene group, 3 -Methoxy-1,4-phenylene group, 3-trifluoromethyl-1,4-phenylene group, 2,5-dimethoxy-1,4-phenylene group, 2,3,5,6-tetrafluoro-1,4 -Phenylene group, 2,3,5,6-tetrachloro-1,4-phenylene group, 3-nitro-1,4-phenylene group, 3-cyano-1,4-phenylene group and the like.

The “optionally substituted aralkylene group having 5 to 12 carbon atoms” usually has 6 or more carbon atoms, usually 10 or less, preferably 9 or less, more preferably 8 or less. is there.
Specific examples of the aralkylene group include, but are not limited to, the aralkylene group as shown in the following group [C].

Is mentioned.
As the substituent that the aralkylene group may have, a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, Isopropyl group, etc.); C1-C10 alkoxy group (eg, methoxy group, ethoxy group, etc.); C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.); C1-C10 acylamino Group (eg, acetamido group, benzoylamide group, etc.); nitro group; cyano group; halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group) , Ethyl group, isopropyl group, etc.), C1-10 alkoxy group (eg, methoxy group, ethoxy group, etc.), C1-10 acyl group (eg, acetyl group, benzoyl group, etc.), carbon An acylamino group having 1 to 10 carbon atoms (eg, acetamido group, benzoylamide group, etc.), a nitro group, an aryl group having 4 to 10 carbon atoms which may have 1 to 3 substituents selected from a cyano group and the like (Eg, phenyl group, naphthyl group, etc.). Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

  Specific examples of the optionally substituted aralkylene group include 2-methyl-1,4-xylylene group, 2,5-dimethyl-1,4-xylylene group, 2-methoxy-1,4-xylylene group, 2 , 5-dimethoxy-1,4-xylylene group, 2,3,5,6-tetrafluoro-1,4-xylylene group, α, α-dimethyl-1,4-xylylene group, α, α, α ′, an α′-tetramethyl-1,4-xylylene group, and the like.

  “Selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Specific examples of the structure in which two or more groups are connected by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group are listed below. Although not limited, it is a divalent group as shown in the following [D] group.

Is mentioned. Among these, it is preferable that two or more groups selected from an alkylene group, an arylene group, or an aralkylene group capable of imparting flexibility while maintaining the transparency and stability of the oligofluorene epoxy resin composition are oxygen. A group in which an alkylene group as shown in the following [E] group is connected with an oxygen atom, which is capable of increasing the glass transition temperature of the resin composition while imparting flexibility. It is.

From the viewpoints of workability and glass transition temperature, when these groups are connected, the number of carbons is preferably 2 or more, more preferably 6 or less, and 4 or less. More preferably.
Among these, a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted carbon number 1 is preferable. 2 or more groups selected from the group consisting of an alkylene group having 10 to 10 carbon atoms, an arylene group having 4 to 10 carbon atoms that may be substituted, and an aralkylene group having 5 to 12 carbon atoms that may be substituted are oxygen atoms , A sulfur atom which may be substituted, a nitrogen atom which may be substituted, or a group connected by a carbonyl group.

  More preferably, a direct bond, a linear alkylene group, an alkylene group containing a branched chain, or a linear or branched alkylene group at any two positions of the alicyclic structure as shown in the group [A] above. An alicyclic alkylene group having a bond, a phenylene group, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, and optionally substituted. Two or more groups selected from the group consisting of aralkylene groups having 5 to 12 carbon atoms are groups linked by an oxygen atom.

  More preferably, there is a tendency that coloring of the cured product can be suppressed by having no aromatic ring, direct bond, methylene group, ethylene group, n-propylene group, n-butylene group, methylmethylene group, 1-methylethylene. Group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group or an alicyclic alkylene group as shown in the following group [F]

(The positions of substitution of two bonds in each ring structure shown in the above [F] group are arbitrary, and two bonds may be substituted on the same carbon).
More preferably, it is a direct bond, a methylene group, an ethylene group, an n-propylene group, an n-butylene group, a methylmethylene group, a 1-methylethylene group, a 2-methylethylene group, or a 2,2-dimethylpropylene group. . Particularly preferred is a methylene group, an ethylene group, or an n-propylene group.

Since the glass transition temperature tends to be low when the chain length is long, short chain groups such as groups having 2 or less carbon atoms are preferred. Furthermore, a methylene group is particularly preferable because it has an advantage that it can be introduced in a short step and industrially at low cost.
On the other hand, an arylene group having 4 to 10 carbon atoms, or an optionally substituted alkylene group having 1 to 10 carbon atoms and optionally substituted, which can increase the glass transition temperature of the oligofluorene epoxy resin composition. A group in which two or more groups selected from the group consisting of an arylene group having 4 to 10 carbon atoms are connected by an oxygen atom is preferable, and a 1,4-phenylene group, a 1,5-naphthylene group, and a 2,6-naphthylene group are preferable. A group or a divalent group as shown in the following [D2] group is more preferable.

In order to obtain desired optical characteristics, it is important to appropriately select the substituents α ¹ and α ² . Preferably, a low photoelastic coefficient required for an optical material can be achieved by having no aromatic ring, direct bond, methylene group, ethylene group, n-propylene group, n-butylene group, methylmethylene group, 1-methyl Ethylene group, 2-methylethylene group, 2,2-dimethylpropylene group, 2-methoxymethyl-2-methylpropylene group, or an alicyclic alkylene group as shown in the above [F] group, or oligofluorene epoxy resin 1,4-phenylene group and 2,6-naphthylene group, which can increase the refractive index of the composition.

More preferred are a methylene group, a direct bond, an ethylene group, an n-propylene group, an n-butylene group, a methylmethylene group, a 1-methylethylene group, a 2-methylethylene group, or a 2,2-dimethylpropylene group.
Still more preferably, they are a methylene group, ethylene group, or n-propylene group. Since the glass transition temperature tends to be low when the chain length is long, short chain groups such as groups having 3 or less carbon atoms are preferred. Furthermore, since the molecular structure becomes small, the ratio of the fluorene ring in the repeating unit can be increased, so that desired optical properties can be efficiently expressed.
A methylene group is particularly preferred because it has an advantage that it can be introduced in a short step and at low cost industrially.
Moreover, it is preferable that the substituents α ¹ and α ² are the same in order to facilitate the production.

<1.4 Specific structure>
As the oligofluorene epoxy resin of the present invention, specifically, those represented by the following general formula (1) (hereinafter sometimes abbreviated as oligofluorene epoxy resin (1)) can be preferably used.

In the formula, R ¹ and R ² are each independently a direct bond, an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms, or a substituted group. An aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10 acyloxy groups, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.

R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5.
In the formula (1), as R ¹ and R ² , those exemplified for <1.3 substituents α ¹ and α ² > can be preferably used.
Similarly, as the alkyl group having 1 to 10 carbon atoms which may be substituted in R ¹⁰ , those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted with <1.2 epoxy group> Can be preferably used.

Specific examples of the “optionally substituted alkyl group having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ include, but are not limited to, a methyl group, an ethyl group, n Linear alkyl groups such as -propyl group, n-butyl group, n-pentyl group, n-hexyl, n-decyl; isopropyl group, 2-methylpropyl group, 2,2-dimethylpropyl group, 2-ethylhexyl An alkyl group containing a branched chain such as a group; and a cyclic alkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The number of carbon atoms in the optionally substituted alkyl group having 1 to 10 carbon atoms is preferably 4 or less, and more preferably 2 or less. Within this range, steric hindrance between fluorene rings is unlikely to occur, and desired optical properties derived from the fluorene ring tend to be obtained.
Examples of the substituent that the alkyl group may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.) C1-10 acyl group (eg, acetyl group, benzoyl group, etc.); C1-10 acylamino group (eg, acetamido group, benzoylamide group, etc.); nitro group; cyano group; halogen atom ( Examples, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), alkoxy group having 1 to 10 carbon atoms (eg, methoxy group) Ethoxy group, etc.), C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.), C1-C10 acylamino group (eg, acetamido group, benzoylamide group, etc.), B group, an aryl group having 1 to 3 substituents which may 4-10 carbon atoms which may have a selected from a cyano group (e.g., phenyl group, naphthyl group etc.) and the like. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

Specific examples of the alkyl group which may be substituted include a trifluoromethyl group, a benzyl group, a 4-methoxybenzyl group, and a methoxymethyl group.
Specific examples of the “optionally substituted aryl group having 4 to 10 carbon atoms” in R ^{4 to} R ⁹ include, but are not limited to, a phenyl group and a 1-naphthyl group. And aryl groups such as 2-naphthyl group; and heteroaryl groups such as 2-pyridyl group, 2-thienyl group and 2-furyl group.

The number of carbon atoms in the optionally substituted aryl group having 4 to 10 carbon atoms is preferably 8 or less, and more preferably 7 or less. Within this range, steric hindrance between fluorene rings is unlikely to occur, and desired optical properties derived from the fluorene ring tend to be obtained.
Examples of the substituent that the aryl group may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, Isopropyl group, etc.); C1-C10 alkoxy group (eg, methoxy group, ethoxy group, etc.); C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.); C1-C10 acylamino Groups (eg, acetamido group, benzoylamide group, etc.); nitro groups; cyano groups, and the like. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

  Specific examples of the aryl group which may be substituted include 2-methylphenyl group, 4-methylphenyl group, 3,5-dimethylphenyl group, 4-benzoylphenyl group, 4-methoxyphenyl group, 4-nitrophenyl. Group, 4-cyanophenyl group, 3-trifluoromethylphenyl group, 3,4-dimethoxyphenyl group, 3,4-methylenedioxyphenyl group, 2,3,4,5,6-pentafluorophenyl group, 4 -A methylfuryl group etc. are mentioned.

Specific examples of the “optionally substituted acyl group having 1 to 10 carbon atoms” in R ^{4 to} R ⁹ include, but are not limited to, a formyl group, an acetyl group, and propionyl. Groups, aliphatic acyl groups such as 2-methylpropionyl group, 2,2-dimethylpropionyl group, 2-ethylhexanoyl group; benzoyl group, 1-naphthylcarbonyl group, 2-naphthylcarbonyl group, 2-furylcarbonyl group, etc. Of the aromatic acyl group.

The number of carbon atoms in the optionally substituted acyl group having 1 to 10 carbon atoms is preferably 4 or less, and more preferably 2 or less. Within this range, steric hindrance between fluorene rings is unlikely to occur, and desired optical properties derived from the fluorene ring tend to be obtained.
Examples of the substituent that the acyl group may have include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom); an alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, An isopropyl group, etc.); an alkoxy group having 1 to 10 carbon atoms (eg, methoxy group, ethoxy group, etc.); an acylamino group having 1 to 10 carbon atoms (eg, acetamido group, benzoylamide group, etc.); a nitro group; Halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), alkyl group having 1 to 10 carbon atoms (eg, methyl group, ethyl group, isopropyl group, etc.), alkoxy group having 1 to 10 carbon atoms (eg, , Methoxy group, ethoxy group, etc.), C1-C10 acyl group (eg, acetyl group, benzoyl group, etc.), C1-C10 acylamino group (eg, acetamido group, benzoylamide) Etc.), a nitro group, an aryl group (e.g. 1 to 3 substituents which may 4-10 carbon atoms which may have a selected from a cyano group, a phenyl group, a naphthyl group, etc.) and the like. Although the number of the said substituent is not specifically limited, 1-3 are preferable. When there are two or more substituents, the types of the substituents may be the same or different. Moreover, it is preferable that it is unsubstituted from a viewpoint that it can manufacture industrially cheaply.

Specific examples of the optionally substituted acyl group include chloroacetyl group, trifluoroacetyl group, methoxyacetyl group, phenoxyacetyl group, 4-methoxybenzoyl group, 4-nitrobenzoyl group, 4-cyanobenzoyl group, 4 -A trifluoromethyl benzoyl group etc. are mentioned.
Specific structures of the “optionally substituted alkoxy group having 1 to 10 carbon atoms, aryloxy group or acyloxy group” in R ^{4 to} R ⁹ are listed below, but are not limited thereto. Examples thereof include alkoxy groups such as methoxy group, ethoxy group, isopropoxy group, t-butoxy group and trifluoromethoxy group; aryloxy groups such as phenoxy group; acyloxy groups such as acetoxy group and benzoyloxy group.

The number of carbon atoms in the optionally substituted alkoxy group having 1 to 10 carbon atoms, aryloxy group or acyloxy group is preferably 4 or less, and more preferably 2 or less. Within this range, steric hindrance between fluorene rings is unlikely to occur, and desired optical properties derived from the fluorene ring tend to be obtained.
Specific examples of the “optionally substituted amino group” in R ^{4 to} R ⁹ include, but are not limited to, an amino group; N-methylamino group, N, N— Dimethylamino group, N-ethylamino group, N, N-diethylamino group, N, N-methylethylamino group, N-propylamino group, N, N-dipropylamino group, N-isopropylamino group, N, N -Aliphatic amino group such as diisopropylamino group; Aromatic amino group such as N-phenylamino group, N, N-diphenylamino group; Formamide group, acetamide group, decanoylamide group, benzoylamide group, chloroacetamide group, etc. An acylamino group such as benzyloxycarbonylamino group, alkoxycarbonylamino group such as tert-butyloxycarbonylamino group, etc. It is.

Among these, N, N-dimethylamino group, N-ethylamino group, or N, N-diethylamino has no proton with high acidity, tends to have a small molecular weight, and can increase the fluorene ratio. Group is preferable, and N, N-dimethylamino group is more preferable.
Specific structures of the “sulfur atom having a substituent” in R ^{4 to} R ⁹ include, but are not limited to, a sulfo group; a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, Alkylsulfonyl groups such as isopropylsulfonyl group; arylsulfonyl groups such as phenylsulfonyl group and p-tolylsulfonyl group; alkylsulfinyl groups such as methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group and isopropylsulfinyl group; phenylsulfinyl group, p -Arylsulfinyl group such as tolylsulfinyl group; alkylthio group such as methylthio group and ethylthio group; arylthio group such as phenylthio group and p-tolylthio group; alkoxysulfonyl group such as methoxysulfonyl group and ethoxysulfonyl group Aryloxysulfonyl group such as phenoxysulfonyl group; aminosulfonyl group; N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N-tert-butylaminosulfonyl group, N, N-dimethylaminosulfonyl group, N, N- Alkylsulfonyl groups such as diethylaminosulfonyl group; arylaminosulfonyl groups such as N-phenylaminosulfonyl group and N, N-diphenylaminosulfonyl group; and the like. The sulfo group may form a salt with lithium, sodium, potassium, magnesium, ammonium or the like.

Among these, a methylsulfinyl group, an ethylsulfinyl group, or a phenylsulfinyl group is preferred because it does not have protons with high acidity, has a low molecular weight, and can increase the fluorene ratio, and is a methylsulfinyl group. It is more preferable.
Examples of the “halogen atom” in R ^{4 to} R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Among these, a fluorine atom, a chlorine atom, or a bromine atom is preferable because it is relatively easy to introduce and has an electron-withdrawing substituent and tends to increase the reactivity at the 9-position of fluorene. More preferably it is an atom.
Adjacent R ^{4 to} R ⁹ may be bonded to each other to form a ring. Specific examples thereof include substituted fluorene structures as shown in the following [G] group.

In this way, by making R ^{4 to} R ⁹ a specific atom or substituent as described above, there is little steric hindrance between the main chain and the fluorene ring or between the fluorene rings, and it is derived from the fluorene ring. There is a tendency that desired optical characteristics can be obtained.
R ^{4 to} R ⁹ are preferably all hydrogen atoms, or R ⁴ and / or R ⁹ is any one selected from the group consisting of halogen atoms, acyl groups, nitro groups, cyano groups, and sulfo groups. R ^{5 to} R ⁸ are hydrogen atoms. In the case of all hydrogen atoms, it can be derived from fluorene which is industrially inexpensive. Further, when R ⁴ and / or R ⁹ is any one selected from the group consisting of a halogen atom, an acyl group, a nitro group, a cyano group, and a sulfo group, and R ^{5 to} R ⁸ are hydrogen atoms, fluorene 9 Since the reactivity of the position is improved, various induction reactions tend to be adaptable. More preferably, they are all hydrogen atoms, or R ⁴ and / or R ⁹ is any one selected from the group consisting of a fluorine atom, a chlorine atom, a bromine atom, and a nitro group, and R ^{5 to} R ⁸ are hydrogen atoms. In particular, the case of all hydrogen atoms is particularly preferred. Moreover, by setting it as said thing, a fluorene ratio can be raised, the steric hindrance of fluorene rings does not produce easily, and there exists a tendency for the desired optical characteristic derived from a fluorene ring to be acquired.

<1.5 Specific Example of Oligofluorene Epoxy Resin>
Specific examples of the oligofluorene epoxy resin of the present invention include structures as shown in the following [H] group.

<1.6 Physical properties of oligofluorene epoxy resin>
Although the physical property value of the oligofluorene epoxy resin of this invention is not specifically limited, It is preferable that the physical property value illustrated below is satisfied.
The chlorine content in the oligofluorene epoxy resin of the present invention is preferably 1000 ppm by mass or less in terms of Cl. Furthermore, it is preferable that it is 100 mass ppm or less. When the content ratio of the chlorine component is large, the chlorine component remains in the obtained cured product, which may reduce the insulation of the cured product or corrode the metal wiring or the like that comes into contact.

  The melting point of the oligofluorene epoxy resin of the present invention is preferably 200 ° C. or lower. Furthermore, it is preferable that it is 180 degrees C or less, and it is especially preferable that it is 150 degrees C or less. When curing the composition, it is usually necessary to heat and melt and mix. However, if the melting point is high, the melting temperature becomes high and the operability deteriorates, and the curing starts before mixing and the quality is stable and uniform. Difficult to obtain a cured product. On the other hand, the lower limit is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. When the melting point is close to room temperature, it may be partially melted and solidified during storage to form a lump or a semi-solid, which makes handling difficult.

  The 150 ° C. melt viscosity of the oligofluorene epoxy resin of the present invention is preferably 10 P or less. Further, it is preferably 4P or less, and particularly preferably 2P or less. When the viscosity is low, mixing of the composition by heating and melting becomes easy, and moldability and workability are improved. Furthermore, it becomes possible to add more fillers, and the physical properties of the cured product can be adjusted.

The refractive index at 589 nm of the oligofluorene epoxy resin of the present invention is preferably 1.60 or more, and more preferably 1.62 or more. Furthermore, it is preferably 1.63 or more, and particularly preferably 1.64 or more. Here, the refractive index is determined by an extrapolation method of DMF solution (method described in Examples described later) assuming that the specific gravity of the oligofluorene epoxy resin of the present invention is 1.2. Since the refractive index is high, it can be made thin and light when used in an optical material such as a lens, and a material having a wide range of refractive index can be obtained by mixing with other materials.

  The oligofluorene epoxy resin of the present invention preferably has 6 or less oxygen atoms. Further, it is preferably 4 or less, and particularly preferably 2 or less oxygen atoms. If there are many oxygen atoms, the water absorption rate of the cured product usually increases and the heat and moisture resistance and dimensional stability deteriorate. Moreover, it is preferable that the number of atoms other than a carbon atom and a hydrogen atom is six or less. Further, it is preferably 4 or less, and particularly preferably 2 or less. Including atoms other than carbon atoms and hydrogen atoms usually increases the water absorption of the cured product, and tends to cause coloration by light.

<1.7 Oligofluorene Epoxy Resin According to Other Embodiment>
From the viewpoint of easy synthesis, in another embodiment, as an oligofluorene epoxy resin, an oligofluorene epoxy resin represented by the following general formula (10) (hereinafter sometimes abbreviated as oligofluorene epoxy resin (10)) Is preferably used.

Wherein, R ⁴ to R ¹⁰ are as defined in the general formula (1). R _i represents a hydrogen atom or a methyl group. n shows the integer value of 1-5.
Moreover, you may use the oligo fluorene epoxy resin represented by the following general formula (14) which includes both general formula (1) and general formula (10).

Wherein, R ¹ to R ¹⁰ are as defined in the general formula (1). n shows the integer value of 1-5.
β ¹ and β ² are each independently a direct bond or an ester bond.
<1.7.1 Specific Example of Oligofluorene Epoxy Resin According to Other Embodiment>
Specific examples of the oligofluorene epoxy resin according to another embodiment include structures as shown in the following [I] group.

<2 Production Method of Oligofluorene Epoxy Resin>
<2.1 Production by oxidation of oligofluorene having a carbon-carbon double bond>
Although it does not specifically limit about the manufacturing method of the oligo fluorene epoxy resin of this invention, The oligo fluorene epoxy resin of this invention can be obtained by oxidizing the oligo fluorene which has the carbon-carbon double bond mentioned later.

  The oxidation method is not particularly limited as long as the oligofluorene epoxy resin of the present invention can be obtained, and can be performed by a known method. For example, the oxidizing agent used in the oxidation reaction includes hydrogen peroxide, peracids, and hydroperoxides. Specifically, in order to suppress the ring-opening reaction of the epoxy group, a method using quaternary ammonium salt and hydrogen peroxide aqueous solution in the presence of tungstic acid (Method A), organic such as peracetic acid and m-chlorobenzoic acid Examples include a method using a peracid (method B), and the method can be selected according to the properties of the compound. In particular, a method of using a quaternary ammonium salt and an aqueous hydrogen peroxide solution in the presence of tungstic acids can use inexpensive hydrogen peroxide as an oxidizing agent, and is preferable from the environmental viewpoint because the by-product is water.

  When oligofluorene having a carbon-carbon double bond has a plurality of carbon-carbon double bonds, the amount of carbon-carbon double bonds can be controlled by controlling the amount of oxidant used, reaction time, and reaction conditions. It can also be left without partial oxidation. That is, the oligofluorene epoxy resin of the present invention and a compound in which an epoxy group is partially substituted with a carbon-carbon double bond can be present at an arbitrary ratio. By allowing a compound in which an epoxy group is partially substituted with a carbon-carbon double bond to coexist, the melting point and viscosity can be lowered, which is preferable from the viewpoint of improving workability.

<2.1.1 Method A: Method Performed with Quaternary Ammonium Salt and Hydrogen Peroxide Solution in the Presence of Tungstic Acids>
Hereinafter, a method (Method A) of oxidizing with a quaternary ammonium salt and an aqueous hydrogen peroxide solution in the presence of tungstic acids will be described.
Examples of the tungstic acid used in the reaction include tungstic acid; phosphotungstic acid such as 12-tungstophosphoric acid and 18-tungstophosphoric acid; borotungstic acid such as 12-tungstoboric acid; silicotungstic acid such as 12-tungstosilicic acid; The salt etc. are mentioned. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations. Examples of counter cations of these salts include quaternary ammonium ions, alkaline earth metal ions, and alkali metal ions.

  Examples of the counter cation include tetramethylammonium ion, benzyltriethylammonium ion, tridecanylmethylammonium ion, dilauryldimethylammonium ion, trioctylmethylammonium ion, trihexadecylmethylammonium ion, trimethylstearylammonium ion, and tetrapentyl. Quaternary ammonium ions such as ammonium ion, cetyltrimethylammonium ion, benzyltributylammonium ion, alkaline earth metal ions such as calcium ion and magnesium ion, alkali metal ions such as lithium ion, sodium ion, potassium ion and cesium ion Can be mentioned.

Among these, tungstic acid, sodium tungstate, calcium tungstate and hydrates thereof are preferable from the viewpoint of availability.
The amount of tungstic acid used is not particularly limited, but is preferably 0.001 equivalent or more, more preferably in terms of catalytic metal atom, per equivalent of carbon-carbon double bond of oligofluorene having a carbon-carbon double bond. Is 0.005 equivalents or more, more preferably 0.01 equivalents or more, and preferably 5 equivalents or less, more preferably 3 equivalents or less, more preferably 1 equivalent or less. When the amount used is less than 0.001 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 5 equivalents, removal of tungstic acids tends to be difficult.

As the quaternary ammonium salt, a quaternary ammonium salt having a total carbon number of 10 or more, preferably 25 to 100, more preferably 25 to 55 can be preferably used, and in particular, the alkyl chain is preferably an aliphatic chain. .
Specifically, tridecanyl methyl ammonium salt, dilauryl dimethyl ammonium salt, trioctyl methyl ammonium salt, trihexadecyl methyl ammonium salt, trimethyl stearyl ammonium salt, tetrapentyl ammonium salt, cetyl trimethyl ammonium salt, benzyl tributyl ammonium salt , Dicetyldimethylammonium salt, tricetylmethylammonium salt and the like. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

Moreover, as an ammonium salt, the ammonium salt indicated by PCT / JP2013 / 059461 and described in Japanese Patent Application No. 2013-207331 can also be used. Specifically, it is preferable to use an ammonium salt having at least one substituent that can be converted into a functional group containing active hydrogen or a salt thereof.
Examples of the counter anion of these ammonium salts include hydrogen sulfate ion, monomethyl sulfate ion, halide ion, nitrate ion, acetate ion, carbonate ion, hydrogen phosphate ion, sulfonate ion, carboxylate ion, and hydroxide. Ions. From the viewpoint that the counter anion is not added to the epoxy or olefin, and preparation is easy, hydrogen sulfate ion, monomethyl sulfate ion, acetate ion, phosphate ion, hydroxide ion are preferable, and trioctylmethylammonium salt of A combination of hydrogen sulfate ions is particularly preferred.

  The amount of quaternary ammonium salt used is not particularly limited, but is preferably 0.01 equivalents or more, more preferably 0.1 equivalents or more, and preferably 10 equivalents or less, more preferably 1 equivalent of tungstic acid. Is 5 equivalents or less. When the amount used is less than 0.01 equivalent, the reaction does not proceed sufficiently, and when the amount used is more than 5 equivalents, removal of the ammonium salt tends to be difficult.

  The concentration of the aqueous hydrogen peroxide solution introduced into the reaction solution is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, and preferably 60% by mass or less, more preferably 50% by mass or less. It is. If the concentration is lower than 10% by mass, the reaction rate and batch efficiency are reduced. If the concentration is higher than 60% by mass, it becomes difficult to control the internal temperature during the reaction, or abnormal decomposition of hydrogen peroxide. Tends to occur and the risk increases.

  The amount of hydrogen peroxide used is not particularly limited, and varies depending on the type of oligofluorene having a carbon-carbon double bond, the type of catalyst, reaction conditions, etc., but the carbon-carbon double of an oligofluorene having a carbon-carbon double bond. It is preferably 1 equivalent or more, more preferably 2 equivalents or more, and preferably 20 equivalents or less, more preferably 10 equivalents or less, in terms of hydrogen peroxide, with respect to 1 equivalent of the bond. If the amount used is less than 1 equivalent, the reaction tends not to proceed sufficiently. If the amount used is more than 20 equivalents, it becomes difficult to control the reaction and ensure safety, and the amount of the reaction solution increases. Productivity tends to decrease.

  In Method A, phosphoric acids may be contained in addition to the tungstic acids, quaternary ammonium salts and aqueous hydrogen peroxide solution. Examples of phosphoric acids include phosphoric acid, polyphosphoric acid, pyrophosphoric acid, sodium phosphate, potassium phosphate, ammonium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate, ammonium hydrogen phosphate, sodium dihydrogen phosphate, phosphorus Examples include inorganic phosphoric acid such as potassium dihydrogen acid and calcium dihydrogen phosphate, and organic phosphonic acid such as aminomethylphosphonic acid and phenylphosphonic acid, and phosphoric acid that is readily available is preferable.

The amount of phosphoric acid used is not particularly limited, and the appropriate amount used varies depending on the type of phosphoric acid used and the type of tungstic acid used. Generally, the equivalent amount of phosphorus contained in the phosphoric acids is
Usually 0.1 equivalents or more, preferably 0.2 equivalents or more, more preferably 0.2 equivalents or more, and usually 5.0 equivalents or less, preferably 1 equivalent or less, based on 1 atom of tungsten in the tungstic acid used. 3.0 equivalent or less, more preferably 2.0 equivalent or less.

A solvent can also be used for the reaction. Although the solvent to be used is not particularly limited, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and dodecane; alcohols such as methanol, ethanol, isopropanol, butanol, hexanol and cyclohexanol Halogenated solvents such as chloroform, dichloromethane and dichloroethane; ethers such as tetrahydrofuran, dioxane, t-butyl methyl ether and cyclopentyl methyl ether; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; acetonitrile, butyronitrile and the like Nitriles; ester compounds such as ethyl acetate, butyl acetate and methyl formate; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Ureas such as N, N′-dimethylimidazolidinone; water and mixtures of these solvents. Among these, water, aromatic hydrocarbons, aliphatic hydrocarbons, and mixtures of these solvents are preferable, and water and toluene having a boiling point higher than the reaction temperature are more preferable, which are stable in the reaction and post-treatment steps. .

In the method A, the reaction is usually performed in a two-layer reaction system in which an aqueous phase and an organic phase are separated. By separating the two layers, it is possible to suppress the epoxy resin from being distributed to the organic phase, and the epoxy ring from being decomposed by ring opening, transition, or the like due to the influence of the acidic aqueous layer.
The use mode of the organic solvent is not particularly limited, but when the oligofluorene having a carbon-carbon double bond used in the reaction is liquid under the reaction conditions, the solvent may not be used. . When the oligofluorene having a carbon-carbon double bond is a solid, it may be dissolved in a solvent or in a suspended state, but it is usually preferable to be dissolved in a solvent under reaction temperature conditions.

The amount of the organic solvent used depends on the solubility of the compound, but the reaction rate often decreases as the amount of the solvent increases. Therefore, it is usually 0 to 10 times, preferably 0, of the oligofluorene having a carbon-carbon double bond. The amount is double to 5 times, more preferably 0 to 3 times.
In Method A, the reaction temperature is not particularly limited as long as the reaction is not inhibited, but is usually 10 ° C to 90 ° C, preferably 35 ° C to 80 ° C, more preferably 60 ° C to 75 ° C. If it is less than the lower limit, the reaction rate may be slow, and if it exceeds the upper limit, it may not be preferable from the viewpoint of safety.

The reaction time varies depending on the reaction scale and the like, but is usually 1 hour or more, preferably 3 hours or more, more preferably 5 hours or more, and usually 48 hours or less, preferably 36 hours or less, more preferably 24 hours or less. It is.
As described above, in Method A, an epoxy compound is produced by oxidizing oligofluorene having a carbon-carbon double bond with a quaternary ammonium salt and an aqueous hydrogen peroxide solution in the presence of tungstic acids. The order of addition of these compounds is not particularly limited, but in a normal reaction, first, in the presence of oligofluorene having a carbon-carbon double bond, tungstic acids, additives such as quaternary ammonium salts and phosphoric acids are added in the reaction solvent. The mixture is mixed with (2), and hydrogen peroxide is added dropwise while taking care of the temperature of the mixture, followed by stirring. After the reaction, the epoxy compound is obtained by performing usual operations such as washing with water, quenching the remaining hydrogen peroxide, and concentrating.

Hydrogen peroxide is quickly consumed in the epoxidation reaction, but it is preferable to add it in several times or continuously from the viewpoint of safety.
In Method A, the reaction can be performed in a two-layer reaction system in which the aqueous phase and the organic phase are separated, so that the ring-opening reaction of the epoxy group can be suppressed, and the oligofluorene epoxy resin is maintained while maintaining high selectivity. Can be synthesized.

<2.1.2 Method B: Method Using Organic Peracids>
Next, a method of oxidizing using organic peracids (Method B) will be described.
Organic peracids used in the reaction include peracetic acid, perpropionic acid, m-chloroperbenzoic acid,
Examples thereof include perbenzoic acid and perphthalic acid. Among these, peracetic acid and m-chloroperbenzoic acid are preferable, and peracetic acid is more preferable because it is industrially inexpensive, liquid, and easy to handle.

Moreover, organic peracids can also be prepared from organic acids and hydrogen peroxide in the reaction system. Examples of organic acids used include acetic acid, propionic acid, m-chlorobenzoic acid, benzoic acid, and phthalic acid. Among these, acetic acid and m-chlorobenzoic acid are preferable, because they are industrially inexpensive and liquid. Acetic acid is more preferable because it is easy to handle.
These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

  The amount of the organic peracid used is not particularly limited, but is preferably 0.5 equivalents or more, more preferably 1 equivalent or more, with respect to 1 equivalent of the carbon-carbon double bond of oligofluorene having a carbon-carbon double bond, More preferably, it is 1.1 equivalents or more, preferably 5 equivalents or less, more preferably 2 equivalents or less, still more preferably 1.5 equivalents or less. When the amount used is less than 1 equivalent, the reaction tends not to proceed sufficiently, and when the amount used is more than 5 equivalents, there is a tendency that the excess organic peracids decompose and cause a reaction runaway.

  Since organic peracids are used in combination with hydrogen peroxide and work catalytically, they may be used in a small amount with respect to hydrogen peroxide, preferably 0.05 equivalents or more, more preferably 0.1 equivalents or more, even more preferably. Is 0.2 equivalents or more, preferably 5 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less. In addition, the amount of hydrogen peroxide used in combination is not particularly limited, but preferably 0.5 equivalent or more with respect to 1 equivalent of the carbon-carbon double bond of oligofluorene having a carbon-carbon double bond, More preferably, it is 1 equivalent or more, More preferably, it is 1.1 equivalent or more, Preferably it is 5 equivalent or less, More preferably, it is 2 equivalent or less, More preferably, it is 1.5 equivalent or less. When the amount used is less than 1 equivalent, the reaction tends not to proceed sufficiently, and when the amount used is more than 5 equivalents, there is a tendency that the excess organic peracids decompose and cause a reaction runaway.

  The concentration of the aqueous hydrogen peroxide solution introduced into the reaction solution is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass, and preferably 60% by mass or less, more preferably 50% by mass or less. is there. If the concentration is lower than 10% by mass, the reaction rate and batch efficiency are reduced. If the concentration is higher than 60% by mass, it becomes difficult to control the internal temperature during the reaction, or abnormal decomposition of hydrogen peroxide. Tends to occur and the risk increases.

A solvent can also be used for the reaction. Although the solvent to be used is not particularly limited, for example, aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic hydrocarbons such as hexane, heptane, dodecane; methanol, ethanol, isopropanol, butanol, hexanol, cyclohexanol, etc. Alcohols such as chloroform, dichloromethane and dichloroethane; ethers such as tetrahydrofuran and dioxane; ketones such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; nitriles such as acetonitrile and butyronitrile; ethyl acetate; Ester compounds such as butyl acetate and methyl formate; organic acids such as acetic acid and propionic acid; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; N, N′-dimethyl Urea such as Midazorijinon; water and mixtures of these solvents. Of these, aromatic hydrocarbons, halogenated solvents and mixtures of these solvents are preferred from the viewpoints of solubility of organic peracids and resistance to oxidation reactions.

  Although the usage-amount of a solvent is not specifically limited, Preferably it is 100 mass parts or more with respect to 100 mass parts of oligo fluorene which has a carbon-carbon double bond, More preferably, it is 200 mass parts or more, Preferably it is 10000 mass. Part or less, more preferably 5000 parts by weight or less. When the amount of the solvent is small, the substrate does not mix well in the system and the reactivity tends to decrease. Moreover, when there are many solvents, the density | concentration of the reaction substrate in a system will fall, and there exists a tendency for reaction rate to fall.

  Although reaction temperature is not specifically limited, Preferably it is 0 degreeC or more, More preferably, it is 20 degreeC or more, Preferably it is 100 degrees C or less, More preferably, it is 80 degrees C or less, More preferably, it is 50 degrees C or less. When it exceeds 100 ° C., decomposition of hydrogen peroxide and hydrolysis of the generated epoxy tend to be promoted. If it is less than 0 ° C., a sufficient reaction rate cannot be obtained, and the reaction tends not to proceed completely.

The reaction time varies depending on the reaction scale and the like, but is usually 1 hour or more, preferably 2 hours or more, and can be selected from the range of usually 72 hours or less, preferably 24 hours or less.
As described above, in Method B, an epoxy resin is produced by oxidizing oligofluorene having a carbon-carbon double bond with organic peracids. The order of addition of these compounds is not particularly limited, but in a normal reaction, oligofluorene having a carbon-carbon double bond is first dissolved or suspended in a reaction solvent, and organic peracids are added while paying attention to the temperature of the mixture. To do. When organic acids and hydrogen peroxide are used in combination, hydrogen peroxide is added after paying attention to the temperature of the mixture after adding the organic acids. After the reaction, normal operations such as washing with water, quenching the remaining peroxide, and concentration are performed to obtain an epoxy resin.

Since organic peracids and hydrogen peroxide may cause rapid reaction and decomposition when the concentration in the system is high, it is preferable to add them in several portions or continuously from the viewpoint of safety. .
In Method B, since oxidation can be performed under neutral to weakly acidic conditions, ring-opening reaction of epoxy groups can be suppressed, and an oligofluorene epoxy resin can be synthesized while maintaining high selectivity.

<2.1.3 Production by addition of epihalohydrin>
In patent document 1, the difluor orange epoxy compound is synthesize | combined using epibromohydrin. In this method, the production of by-products having a bromine atom is inevitable, and purification such as column chromatography is necessary to obtain a high-purity product.

<2.1.4 Manufacture by addition of acrylate>
Hereinafter, the production method of the oligofluorene epoxy resin represented by the following general formula (10) will be described separately as Production Method C and Production Method D.

In formula, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹¹ is an organic substituent having 1 to 10 carbon atoms. R _i represents a hydrogen atom or a methyl group. n shows the integer value of 1-5.

<2.1.4.1 Production Method C: Production Method by Transesterification (Step ii) via Michael Addition Reaction (Step ia)>
The oligofluorene epoxy resin of the present invention represented by the general formula (10) is a raw material of an oligofluorene compound represented by the general formula (8) (hereinafter sometimes abbreviated as oligofluorene compound (8)). After synthesizing an oligofluorester represented by the general formula (9) by the Michael addition reaction (step ia) (hereinafter sometimes abbreviated as oligofluorene compound (9)), the ester exchange reaction (step ii) Can be manufactured.

<2.1.4.1.1 Step ia: Michael addition reaction>
The oligofluor orange ester (9) is prepared in the presence of a base in the presence of a base in the presence of a base, with an oligofluorene compound (8) and a (meth) acrylic acid ester (hereinafter referred to as (meth) acrylic acid ester (hereinafter referred to as (meth) acrylic acid ester ( 11), which may be abbreviated as 11).

In formula, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹¹ is an organic substituent having 1 to 10 carbon atoms. R _i represents a hydrogen atom or a methyl group. n shows the integer value of 1-5.

<2.1.4.1.1.1 (Meth) acrylic acid ester>
(Meth) acrylic acid ester as a reaction reagent is one represented by the general formula (11) in step (ia), in the general formula (11), R _i represents a hydrogen atom or a methyl group.

As (meth) acrylic acid ester (11), methyl acrylate, ethyl acrylate, phenyl acrylate, allyl acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, 1,4-cyclohexane Acrylic acid esters such as dimethanol monoacrylate, and methacrylic acid esters such as methyl methacrylate, ethyl methacrylate, phenyl methacrylate, allyl methacrylate, glycidyl methacrylate, and 2-hydroxyethyl methacrylate.

R ¹¹ is smaller, industrially inexpensive, easy to purify by distillation, and highly reactive. Therefore, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, phenyl acrylate, or phenyl methacrylate is used. Particularly preferred.
Two or more different (meth) acrylic acid esters (11) may be used, but it is preferable to use one kind of (meth) acrylic acid ester (11) from the viewpoint of simplicity of purification.

  Since the (meth) acrylic acid ester (11) has a high polymerization activity, when it is present at a high concentration, it tends to be easily polymerized by external stimuli such as light, heat, and acid / base. At that time, it may be very dangerous because it generates a large amount of heat. Therefore, it is better not to use the amount of (meth) acrylic acid ester (11) too much from the viewpoint of safety. Usually, it is 10 times mol or less with respect to the oligo fluorene compound (8) which is a raw material, Preferably it is 5 times mol or less, More preferably, it is 3 times mol or less. The lower limit is usually 2 times mol or more since the theoretical amount is 2 times mol with respect to the raw material. In order to accelerate the progress of the reaction and prevent the raw materials and intermediates from remaining, the amount of the methacrylic acid ester (11) used is preferably 2.2 times mol or more, more preferably relative to the raw material oligofluorene compound (8). Is 2.5 times mole or more.

<2.1.4.1.1.2 Base>
Bases include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, sodium carbonate, sodium bicarbonate and potassium carbonate. Alkali metal carbonates, alkaline earth metal carbonates such as magnesium carbonate, calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate, potassium phosphate, n-butyl lithium, tertiary butyl lithium, etc. Alkali metal alkoxide salts such as organic lithium salts, sodium methoxide, sodium ethoxide, potassium tertiary butoxide, alkali metal hydrides such as sodium hydride and potassium hydride, triethylamine, diazabicycloundecene, etc. Third grade , Tetramethylammonium hydroxide, tetrabutylammonium hydroxide, quaternary ammonium hydroxides such as benzyltrimethylammonium hydroxide used. These may be used alone or in combination of two or more.

  The oligofluorene compound (8) is easily decomposed in the presence of a base in a solvent. Therefore, it is preferable to use a water-soluble inorganic base because side reactions such as a decomposition reaction can be suppressed when the reaction is performed in a two-layer system of an organic layer and an aqueous layer. Among these, an aqueous solution of an alkali metal hydroxide is preferable from the viewpoint of cost and reactivity, an aqueous solution of sodium hydroxide or an aqueous solution of potassium hydroxide is more preferable, and an aqueous solution of sodium hydroxide is more preferable.

The concentration of the aqueous solution is usually 10 wt / wt% or more, preferably 30 wt / wt% or more, since the reaction rate tends to decrease remarkably when the concentration is low when a particularly preferable sodium hydroxide aqueous solution is used. It is particularly preferable to use an aqueous solution of 40 wt / wt% or more.
The amount of the base used is not particularly limited with respect to the oligofluorene compound (8) as the raw material, but it is particularly preferable because the use of too much amount may increase the purification load after stirring or reaction. When a sodium hydroxide aqueous solution of 40 wt / wt% or more as a base is used, it is usually 10 times volume or less, preferably 5 times volume or less, more preferably 2 times volume with respect to the oligofluorene compound (8). It is as follows. When the amount of the base is too small, the reaction rate is remarkably reduced. Therefore, the base is usually 0.1 times volume or more with respect to the raw material oligofluorene compound (8). Preferably, it is 0.2 times volume or more, more preferably 0.5 times volume or more.

<2.1.4.1.1.3 Phase transfer catalyst>
In the step (ia), when a reaction in a two-layer system of an organic layer and an aqueous layer is performed, it is preferable to use a phase transfer catalyst in order to increase the reaction rate.
Examples of the phase transfer catalyst include tetramethylammonium chloride, tetrabutylammonium bromide, methyltrioctylammonium chloride, methyltridecylammonium chloride, benzyltrimethylammonium chloride, trioctylmethylammonium chloride, tetrabutylammonium iodide, acetyltrimethylammonium bromide, Quaternary ammonium salt halides (excluding fluorine) such as benzyltriethylammonium chloride, N, N-dimethylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium iodide, N-butyl-N-methylpyrrolidi Quaternary pyrrolidinium salts such as nitrobromide, N-benzyl-N-methylpyrrolidinium chloride, N-ethyl-N-methylpyrrolidinium bromide Of quaternary morpholinium salts such as id (excluding fluorine), N-butyl-N-methylmorpholinium bromide, N-butyl-N-methylmorpholinium iodide, N-allyl-N-methylmorpholinium bromide Halide (excluding fluorine), N-methyl-N-benzylpiperidinium chloride, N-methyl-N-benzylpiperidinium bromide, N, N-dimethylpiperidinium iodide, N-methyl-N-ethylpi Examples thereof include halides (excluding fluorine) of quaternary piperidinium salts such as peridinium acetate and N-methyl-N-ethylpiperidinium iodide, and crown ethers. Preferably it is a quaternary ammonium salt, More preferably, it is benzyltrimethylammonium chloride or benzyltriethylammonium chloride.

These may be used alone or in combination of two or more.
If the amount of the phase transfer catalyst used is too large relative to the raw material oligofluorene compound (8), side reactions such as ester hydrolysis and successive Michael reactions tend to become remarkable, and the cost is low. Also from the viewpoint, it is usually 5 times or less, preferably 2 times or less, more preferably 1 time or less, with respect to the oligofluorene compound (8). Since the reaction rate tends to decrease remarkably when the amount of the phase transfer catalyst used is too small, the amount of use of the phase transfer catalyst is usually 0.01 times mol or more with respect to the raw material oligofluorene compound (8). is there. Preferably, it is 0.1 times mole or more, more preferably 0.5 times mole or more.

<2.1.4.1.4 Solvent>
Step (ia) is preferably performed using a solvent.
Specific usable solvents include alkyl nitrile solvents such as acetonitrile and propionitrile, ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, Linear esters such as propyl acetate, phenyl acetate, methyl propionate, ethyl propionate, propyl propionate, phenyl propionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl lactate, ethyl lactate; Cyclic esters such as γ-butyrolactone and caprolactone; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol -Ether solvents such as monomethyl ether acetate, propylene glycol-1-monoethyl ether acetate, etc. Examples of ether solvents include diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tertiary butyl methyl ether, and the like. Examples of system solvents include 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, and examples of halogen-based aromatic hydrocarbons include amide solvents such as chlorobenzene and 1,2-dichlorobenzene. N, N-dimethylformamide, N, N-dimethylacetamide, etc., sulfoxide solvents such as dimethyl sulfoxide, sulfolane, etc., cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane Monocyclic aliphatic hydrocarbons such as hexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1 , 4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Cyclic aliphatic hydrocarbons: acyclic such as n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane Examples of aliphatic hydrocarbons and aromatic hydrocarbons include toluene, p-xylene, o-xylene, and m-xylene. Examples of aromatic heterocycles include pyridine. Examples of alcohol solvents include methanol, ethanol, isopropanol, and n. -Butanol, tertiary butanol, hexanol, octanol, cyclohexanol and the like.

  It has been found that by using a solvent that is phase-separated from water, side reactions such as a decomposition reaction of the oligofluorene compound (8) tend to be suppressed. Furthermore, when a solvent that dissolves the raw material oligofluorene compound (8) well is used, the progress of the reaction tends to be good. Therefore, the solubility of the raw material oligofluorene compound (8) is 0.5 mass%. It is preferable to use the above solvent, more preferably 1.0% by mass or more, and particularly preferably 1.5% by mass or more. Specifically, a halogenated aliphatic hydrocarbon, a halogenated aromatic hydrocarbon, an aromatic hydrocarbon, or an ether solvent is preferable, and dichloromethane, chlorobenzene, chloroform, 1,2-dichlorobenzene, tetrahydrofuran, 1,4- Dioxane or methylcyclopentyl ether is particularly preferred.

These solvents may be used alone or in combination of two or more.
The upper limit of the amount of the solvent used is not particularly limited, but considering the production efficiency of the target product per reactor, it is usually 20 times the volume of the raw material oligofluorene compound (8), preferably 15 times the volume, More preferably, the amount is 10 times the volume. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes poor and stirring becomes difficult and the reaction proceeds slowly. Therefore, the lower limit is usually 1 times that of the raw material oligofluorene compound (8). A volume is used, preferably 2 times volume, more preferably 4 times volume.

<2.1.4.1.1.5 Reaction format>
When carrying out step (ia), the type of reaction can be adopted without any limitation, whether it is a batch type reaction, a flow type reaction or a combination thereof.
In the case of the batch type, the method of charging the reaction reagent into the reactor is that (meth) acrylic acid ester (11) is present in a high concentration when (meth) acrylic acid ester (11) is charged by batch addition at the start of the reaction. For this reason, the polymerization reaction as a side reaction tends to proceed. Therefore, after adding the raw material oligofluorene compound (8), the phase transfer catalyst, the solvent and the base, it is preferable to add the (meth) acrylic acid ester (11) in small portions.

<2.1.4.1.1.6 Reaction conditions>
In step (ia), if the temperature is too low, a sufficient reaction rate cannot be obtained. Conversely, if the temperature is too high, the polymerization reaction of (meth) acrylate ester (11) tends to proceed. It is. Therefore, specifically, the reaction temperature is usually carried out at a lower limit of 0 ° C., preferably 10 ° C., more preferably 15 ° C. On the other hand, the upper limit is usually 40 ° C., preferably 30 ° C., more preferably 20 ° C.
As for the general reaction time in the step (ia), the lower limit is usually 30 minutes, preferably 1 hour, more preferably 2 hours, and the upper limit is not particularly limited, but is usually 20 hours, preferably 10 hours, more preferably 5 hours. It's time.

<2.1.4.1.1.7 Separation and purification of target product>
After completion of the reaction, the oligofluor orange ester (9) is a method of concentrating the solvent after filtering off the by-produced metal halide and remaining inorganic base from the reaction solution, or adding the poor solvent of the target product The method can be used to isolate the target product by precipitating the oligofull orange ester (9).

Moreover, after completion | finish of reaction, you may extract by adding acidic water and the solvent in which the oligo fluor orange ester (9) which is a target object is soluble to a reaction liquid. The target product extracted with a solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.
The solvent that can be used for the extraction is not particularly limited as long as it can dissolve the target oligofluorange ester (9), but is not limited, but includes aromatic hydrocarbon compounds such as toluene and xylene, dichloromethane, One or two or more halogen solvents such as chloroform are preferably used.

  The oligofluorange ester (9) obtained here may be used in the next reaction as it is, or may be used after purification. As the purification method, a usual purification method such as recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be used without limitation. Moreover, it is also possible to melt | dissolve oligo fluor orange ester (9) in a suitable solvent, and to process with activated carbon. The solvent that can be used in this case is the same as the solvent that can be used for extraction.

<2.1.4.1.2 Step (ii): Transesterification>
The oligofluorene epoxy resin (10) has an oligofluor orange ester (9) and an alcohol having an epoxy group represented by the following general formula (12) (hereinafter referred to as an epoxy group) in the presence of a base according to the step (ii). Produced by reacting alcohol (may be abbreviated as alcohol (12)).

In formula, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹¹ is an organic substituent having 1 to 10 carbon atoms. R _i represents a hydrogen atom or a methyl group. n shows the integer value of 1-5.

<2.1.4.1.2.1 Alcohol having an epoxy group>
The alcohol having an epoxy group used in the step (ii) is represented by the general formula (12) in the step (ii). In the general formula (12), R ¹⁰ is an alkyl group having 1 to ¹⁰ carbon atoms. Represents. Specific examples include glycidol, 2-methyl glycidol, 2-ethyl glycidol and the like.

Among these, glycidol and 2-methylglycidol are preferable from the viewpoint of reactivity and cost, and glycidol is particularly preferable.
In step (ii), alcohol (12) having two or more different epoxy groups can be used, but from the viewpoint of simplicity of purification, alcohol (12) having one kind of epoxy group is usually used. It is done.

The amount of the epoxy group-containing alcohol (12) used tends to be a competitive reaction between the alcohol generated from the organic substituent of the ester group of the raw material oligo-fluor orange ester (9) and the alcohol (12) having an epoxy group. Therefore, the reaction proceeds faster when the amount of the alcohol (12) having an epoxy group is larger.
Therefore, the usage-amount of the alcohol (12) which has an epoxy group is 3 times mole or more normally with respect to oligo fluor orange ester (9), Preferably it is 10 times mole or more, More preferably, it is 50 times mole or more.
The alcohol (12) having an epoxy group may be added all at the time of preparation, or may be added in portions as the reaction proceeds.

<2.1.4.1.2.2 Base>
Examples of the base used in step (ii) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, and sodium carbonate. Alkali metal carbonates such as sodium hydrogen carbonate and potassium carbonate, alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, n-butyl Organic lithium salts such as lithium and tertiary butyl lithium, alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, alkali metal hydrides such as sodium hydride and potassium hydride, tetramethyl Ammonium hydroxide De, quaternary ammonium hydroxides such as tetrabutylammonium hydroxide is used.

These may be used alone or in combination of two or more.
Of these, alkali metal alkoxides are preferable from the viewpoint of cost and reactivity, and sodium methoxide or sodium ethoxide is more preferable.
There is no particular upper limit for the amount of base used relative to the raw material oligofluor orange ester (9). However, if the amount used is too large, the purification load after stirring and reaction tends to increase. It is 10 times mol or less of orange ester (9), Preferably it is 5 times mol or less, More preferably, it is 1 time mol or less.
On the other hand, if the amount of the base used is too small, the progress of the reaction tends to be slow. Therefore, the lower limit is usually 0.01 times mol or more, preferably 0. It is 05 times mole or more, more preferably 0.1 times mole or more.

<2.1.4.1.2.3 Solvent>
The step (ii) may be carried out without a solvent, but when the raw material oligofluor orange ester (9) has low solubility in the alcohol (12) having an epoxy group as a reaction reagent and the reactivity is low, a solvent is used. May be used.
Specific usable solvents include alkyl nitrile solvents such as acetonitrile and propionitrile, and ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, tertiary butyl methyl ether, Diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, etc., halogen solvents such as 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane, etc. Halogen aromatic hydrocarbons such as chlorobenzene 1,2-dichlorobenzene and the like as amide solvents, N, N-dimethylformamide, N, N-dimethylacetamide and the like, and sulfoxide solvents as dimethyl sulfoxide and sulfo Cyclic aliphatic hydrocarbons such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc .; their derivatives methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane 1,3,5-trimethylcyclohexane, etc .; polycyclic aliphatic hydrocarbons such as decalin; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nona Examples of non-cyclic aliphatic hydrocarbons and aromatic hydrocarbons such as toluene, n-decane, n-dodecane, and n-tetradecane include toluene, p-xylene, o-xylene, and m-xylene.

  In particular, when a solvent having high solubility of both the raw material oligo-fluor orange ester (9) and the epoxy group-containing alcohol (12) is used, the reaction tends to progress well. Are preferred, and diethylene glycol dimethyl ether or triethylene glycol dimethyl ether is particularly preferred because reaction at a high temperature is possible.

These solvents may be used alone or in combination of two or more.
The upper limit of the amount of the solvent used is not particularly limited, but considering the production efficiency of the target product per reactor, it is usually 20 times volume, preferably 15 times volume of the raw material oligo-fluor orange ester (9). More preferably, the amount is 10 times the volume. On the other hand, if the amount of the solvent used is too small, the solubility of the reagent becomes poor and stirring becomes difficult and the reaction proceeds slowly. Therefore, the lower limit is usually 1 of the raw material oligofull orange ester (9). A volume that is double volume, preferably double volume, and more preferably quadruple volume is used.

<2.1.4.1.2.4. Reaction format>
When carrying out step (ii), the type of reaction can be employed without any limitation, whether it is a batch type reaction, a flow type reaction or a combination thereof.

<2.1.4.1.2.5. Reaction conditions>
When water is contained in the alcohol (12) having an epoxy group as a solvent or a reaction reagent, hydrolysis of the ester proceeds, and as a by-product, there is a tendency to generate a carboxylic acid according to the amount of water contained. is there.
Therefore, the alcohol (12) having an epoxy group, which is a solvent or a reaction reagent, is anhydrous or is not involved in a reaction such as toluene or xylene before the reaction, and is azeotropically dehydrated with a solvent azeotropic with water. It is preferable to carry out the reaction after carrying out the reaction.

In step (ii), if the temperature is too low, there is a tendency that a sufficient reaction rate cannot be obtained. Therefore, specifically, the reaction temperature is usually 20 ° C., preferably 50 ° C., more preferably 80 ° C. Will be implemented. On the other hand, the upper limit is usually 150 ° C., preferably 120 ° C., more preferably 100 ° C.
The lower limit of the general reaction time in step (ii) is usually 2 hours, preferably 4 hours, more preferably 6 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, more preferably 10 hours. It's time.

<2.1.4.1.2.6. Separation and purification of target products>
After completion of the reaction, the target oligofluorene epoxy resin (10) is a method of concentrating the solvent after removing insolubles such as by-produced metal halide and remaining inorganic base from the reaction solution by filtration. Alternatively, it can be isolated by precipitating the oligofluorene epoxy resin (10), which is the target, by employing a method of adding a poor solvent for the target.

Moreover, after completion | finish of reaction, you may extract by adding acidic water and the solvent in which the oligo fluorene epoxy resin (10) which is a target object is soluble to a reaction liquid. The target product extracted with a solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.
Moreover, the carboxylic acid which is a by-product can be removed by wash | cleaning the target object extracted with the solvent with aqueous solution, such as sodium carbonate and potassium carbonate.

The solvent that can be used for the extraction is not particularly limited as long as the target oligofluorene epoxy resin (10) can be dissolved, but is not limited thereto, such as ester solvents such as ethyl acetate, toluene, xylene, and the like. One or more of aromatic hydrocarbon compounds, halogen solvents such as dichloromethane and chloroform are preferably used.
The oligofluorene epoxy resin (10) can be used for curing as it is, or may be used for the next step after purification. As a purification method, usual purification methods such as recrystallization, reprecipitation method, extraction purification and the like can be employed without limitation. Alternatively, the oligofluorene epoxy resin (10) can be dissolved in a suitable solvent and treated with activated carbon. The solvent that can be used in this case is the same as the solvent that can be used for extraction.

<2.1.4.2 Production Method D: Production Method by Michael Addition Reaction (Step ib)>
The oligofluorene epoxy resin of the present invention represented by the general formula (10) is a (meth) acrylic acid ester having an oligofluorene compound (8) and an epoxy group represented by the following general formula (13) in the presence of a base. (Hereinafter, it may be abbreviated as (meth) acrylic acid ester (13) having an epoxy group).

In formula, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R _i represents a hydrogen atom or a methyl group. n shows the integer value of 1-5.
Production Method D uses (meth) acrylic acid ester (13) having an epoxy group instead of (meth) acrylic acid ester (11), and <2.1.4.1.1 Step ia: Michael addition It can manufacture by performing on the conditions similar to reaction>.

The (meth) acrylic acid ester having an epoxy group as a reaction reagent is represented by the general formula (13) in the step (ib). In the general formula (13), R _i represents a hydrogen atom or a methyl group. To express.
As (meth) acrylic acid ester (13) having an epoxy group, glycidyl acrylate, glycidyl methacrylate, 2-methylglycidyl acrylate, 2-methylglycidyl methacrylate, 2-ethylglycidyl acrylate, 2-ethylglycidyl methacrylate Etc.

R ¹⁰ is particularly preferably glycidyl acrylate or glycidyl methacrylate, because a hydrogen atom is industrially inexpensive, easily distilled and purified, and has high reactivity.
(Meth) acrylic acid ester (13) having two or more different epoxy groups may be used, but for ease of purification, (meth) acrylic acid ester (13) having one kind of epoxy group is used. Is preferred.

<3 Oligofluorene having a carbon-carbon double bond>
The oligofluorene having a carbon-carbon double bond of the present invention is used as a raw material in the production method of the oligofluorene epoxy resin of the present invention, and its structure is represented by the following general formula (2) (hereinafter, And may be abbreviated as oligofluorene (2) having a carbon-carbon double bond).

Wherein, R ^1, R ^2, and R ⁴ to R ¹⁰ are as defined in the general formula (1). n shows the integer value of 1-5.
In the formula (2), as R ¹ and R ² , those exemplified for <1.3 substituents α ¹ and α ² > can be preferably used.
Similarly, as the alkyl group having 1 to 10 carbon atoms which may be substituted in R ¹⁰ , those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted with <1.2 epoxy group> And R ^{4 to} R ⁹ are preferably those exemplified in <1.4 Specific Structure>.

The oligofluorene (2) having a carbon-carbon double bond of the present invention is not only a useful raw material for the oligofluorene epoxy resin (1) of the present invention, but also an oligofluorene (2) having a carbon-carbon double bond (2). ) Itself is also useful as a curable resin composition. The oligofluorene (2) having a carbon-carbon double bond of the present invention also has a high refractive index and a melting point similar to the oligofluorene epoxy resin (1) of the present invention because the cross-linking group is a methylene group. Since it is low, it is expected to be excellent in workability.
Moreover, when a crosslinking group is a methylene group, it can manufacture on mild conditions using an inexpensive raw material compared with another crosslinking group.

<3.1 Specific Example of Oligofluorene Having Carbon-Carbon Double Bond>
Specific examples of the oligofluorene having a carbon-carbon double bond of the present invention include structures shown in the following [J] group.

<3.2 Physical properties of oligofluorene having carbon-carbon double bond>
Although the physical property value of the oligofluorene having a carbon-carbon double bond of the present invention is not particularly limited, it is preferable that the physical property value exemplified below is satisfied.
The chlorine content in the oligofluorene having a carbon-carbon double bond of the present invention is preferably 1000 ppm by mass or less in terms of Cl. Furthermore, it is preferable that it is 100 mass ppm or less. When the content ratio of the chlorine component is large, the chlorine component remains in the obtained cured product, which may reduce the insulation of the cured product or corrode the metal wiring or the like that comes into contact.

  The melting point of oligofluorene having a carbon-carbon double bond of the present invention is preferably 170 ° C. or lower. Furthermore, it is preferable that it is 150 degrees C or less, and it is especially preferable that it is 120 degrees C or less. When curing the composition, it is usually necessary to heat and melt and mix. However, if the melting point is high, the melting temperature becomes high and the operability deteriorates, and the curing starts before mixing and the quality is stable and uniform. Difficult to obtain a cured product. On the other hand, the lower limit is preferably 30 ° C. or higher, more preferably 40 ° C. or higher, and particularly preferably 50 ° C. or higher. When the melting point is close to room temperature, it may be partially melted and solidified during storage to form a lump or a semi-solid, which makes handling difficult.

  The oligofluorene having a carbon-carbon double bond of the present invention preferably has a 150 ° C. melt viscosity of 10 P or less. Furthermore, it is preferably 4P or less, and particularly preferably 1P or less. When the viscosity is low, mixing of the composition by heating and melting becomes easy, and moldability and workability are improved. Furthermore, it becomes possible to add more fillers, and the physical properties of the cured product can be adjusted.

The refractive index at 589 nm of the oligofluorene having a carbon-carbon double bond of the present invention is preferably 1.60 or more, and more preferably 1.63 or more. Further, it is preferably 1.65 or more, and particularly preferably 1.66 or more. Here, the refractive index was obtained by extrapolating a DMF solution (method described in Examples described later) assuming that the specific gravity of the oligofluorene having a carbon-carbon double bond of the present invention is 1.2. Is. Since the refractive index is high, it can be made thin and light when used in an optical material such as a lens, and a material having a wide range of refractive index can be obtained by mixing with other materials.

  The oligofluorene having a carbon-carbon double bond of the present invention preferably has 4 or less oxygen atoms. Further, it is preferably 2 or less, and particularly preferably has no oxygen atom. If there are many oxygen atoms, the water absorption rate of the cured product usually increases and the heat and moisture resistance and dimensional stability deteriorate. Moreover, it is preferable that the number of atoms other than a carbon atom and a hydrogen atom is 4 or less. Furthermore, it is preferable that it is 2 or less, and it is preferable that it consists only of a carbon atom and a hydrogen atom especially. Including atoms other than carbon atoms and hydrogen atoms usually increases the water absorption of the cured product, and tends to cause coloration by light.

<3.3 Method for producing oligofluorene having a carbon-carbon double bond>
Although the manufacturing method of the oligo fluorene (2) which has a carbon-carbon double bond of this invention is not limited at all, For example, it can manufacture by the method shown by a following formula.

In formula, R < ¹ >, R < ² >, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). n shows the integer value of 1-5. X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine), a mesyl group, or a tosyl group.

<3.2.1 Step (iii): Production Method of Oligofluorene Compound (II)>
Oligofluorene compounds having a methylene bridge represented by the following general formula (II) (hereinafter sometimes abbreviated as oligofluorene compounds (II)) are fluorenes represented by the following general formula (I) (hereinafter, Fluorenes (I) may be abbreviated) and formaldehydes in the presence of a base in a solvent according to the reaction represented by the following formula.

In formula, R < ⁴ > -R < ⁹ > and n are synonymous with the said Formula (1).

<3.3.1.1 Formaldehydes>
The formaldehydes used in step (iii) are not particularly limited as long as they are substances capable of supplying formaldehyde into the reaction system, and examples thereof include gaseous formaldehyde, formaldehyde aqueous solution, paraformaldehyde polymerized with formaldehyde, and trioxane. Among these, it is particularly preferable to use paraformaldehyde because it is industrially inexpensive and powdery, so that operability is easy and accurate weighing is possible.

(Definition of theoretical quantity)
When the target n number of oligofluorene compounds (II) are produced, the theoretical amount (molar ratio) of formaldehyde with respect to the raw material fluorenes (I) is represented by n / (n + 1).

(Reason why it is better not to exceed the theoretical amount)
When formaldehydes in excess of the theoretical amount are used with respect to the fluorenes (I), the desired oligofluorene compound (II) having a number of n or more tends to be formed. As the number of n increases, the solubility decreases. Therefore, it is known that the purification load tends to increase when the target oligofluorene compound (II) having a number of n or more is present. Therefore, usually, the amount of formaldehyde used is preferably n / (n + 1) times mol or less of the theoretical amount corresponding to the target n number.

(Reason why it is better not to be much lower than the theoretical amount)
Further, when the amount of formaldehyde used is significantly lower than the theoretical amount n / (n + 1), the target oligofluorene compound (II) having a number of n or less becomes the main product, or the raw material fluorenes (I ) Remains unreacted, and it has been found that the yield tends to decrease greatly.

Therefore, the optimal amount of formaldehyde used is, specifically, when n = 1, usually 0.1 times mol or more, preferably 0.3 times mol or more, more preferably fluorenes (I). The amount is 0.38 times mol or more, usually 0.5 times mol or less, preferably 0.46 times mol or less, more preferably 0.42 times mol or less.
When n = 2, it is usually 0.5 times mol or more, preferably 0.55 times mol or more, more preferably 0.6 times mol or more, and usually 0.66 times mol or less, preferably 0.65. Double mole or less, more preferably 0.63 mole or less. As described above, it is known that the structure of the main product and the ratio of the product greatly change according to the amount of formaldehyde used. Several oligofluorene compounds (II) can be obtained in high yield.

<3.3.1.2 Base>
Examples of the base used in the step (iii) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, and sodium carbonate. Alkali metal carbonates such as sodium hydrogen carbonate and potassium carbonate, alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, n-butyl Organic lithium salts such as lithium and tertiary butyl lithium, alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, alkali metal hydride salts such as sodium hydride and potassium hydride, triethylamine, Diazabicik Tertiary amines such as undecene, tetramethylammonium hydroxide, as quaternary ammonium hydroxides such as tetrabutylammonium hydroxide is used. These may be used alone or in combination of two or more.

  Among these, preferred are alkali metal alkoxides having sufficient basicity in this reaction, and more preferred are sodium methoxide and sodium ethoxide which are industrially inexpensive. Here, as the alkali metal alkoxide, a powdery one or a liquid one such as an alcohol solution may be used. Moreover, you may prepare by making an alkali metal and alcohol react.

  The amount of the base used is not particularly limited with respect to the fluorenes (I) as the raw material, but if the amount used is too large, the purification load after stirring and reaction becomes large. Double mole or less, preferably 5 moles or less, more preferably 1 mole or less. On the other hand, if the amount of the base used is too small, the progress of the reaction is slowed. Therefore, the lower limit is usually 0.01 times mol or more, preferably 0.1 times mol or more, relative to the raw material fluorenes (I), More preferably, it is 0.2 times mole or more.

<3.3.1.3 Solvent>
Step (iii) is desirably performed using a solvent. Specific examples of usable solvents include alkyl nitrile solvents such as acetonitrile and propionitrile, and ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and tertiary butyl methyl ether. As halogen solvents, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane and the like, and as halogenated aromatic hydrocarbons, amides such as chlorobenzene and 1,2-dichlorobenzene, etc. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. Examples of the sulfoxide solvent include dimethyl sulfoxide and sulfolane. Examples of the cyclic aliphatic hydrocarbon include cyclopenta. Monocyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Polycyclic aliphatic hydrocarbons; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane, etc. Examples of acyclic aliphatic hydrocarbons and aromatic hydrocarbons include toluene, p-xylene, o-xylene, and m-xylene. Examples of alcohol solvents include methanol, ethanol, isopropanol, n-butanol, tertiary butanol, Examples include hexanol, octanol, and cyclohexanol.

  Among them, an amide solvent or a sulfoxide solvent, which is a polar solvent, is preferable because the solubility of the anion generated from the fluorenes (I) tends to be high and the reaction proceeds favorably. Among them, N, N-dimethylformamide is particularly preferable when the oligofluorene compound (II) with n = 1 or 2 is produced. This is because the solubility of n = 1 or 2 oligofluorene in N, N-dimethylformamide is low, and the desired product precipitates quickly after formation, and further progress of the reaction is suppressed. This is because of a tendency to increase.

These solvents may be used alone or in combination of two or more.
The oligofluorene compound (II) produced in the step (iii) has been found to decrease in solubility in a solvent as the value of n increases, and the generated target product quickly precipitates. It is thought that the progress of the reaction is suppressed. Therefore, it is preferable that the amount of the solvent used is appropriately adjusted according to the value of n. In particular, when the oligofluorene compound (II) having n = 1 or 2 is produced, it is better not to use an excessive solvent in order to increase the selectivity of the target product. For example, when N, N-dimethylformamide, which is the most preferable solvent, is used, the upper limit of the amount of solvent is usually 10 times the volume of the raw material fluorenes (I), preferably 7 times the volume, more preferably 4 An amount that is a double volume is used. On the other hand, if the amount of the solvent used is too small, stirring becomes difficult and the progress of the reaction slows. Therefore, the lower limit is usually 1-fold volume, preferably 2-fold volume, of the raw material fluorenes (I), More preferably, the amount is 3 times the volume.

<3.3.1.4 Reaction format>
When carrying out step (iii), the type of reaction can be employed without any limitation, whether it is a batch type reaction, a flow type reaction or a combination thereof.

<3.3.1.5 Reaction conditions>
Step (iii) may be appropriately adjusted according to the target n-valued oligofluorene compound (II). In order to suppress the progress of the reaction beyond the target n value, it is preferable to perform the reaction at as low a temperature as possible. On the other hand, if the temperature is too low, a sufficient reaction rate may not be obtained.

Therefore, when N, N-dimethylformamide, which is the optimum solvent, and sodium ethoxide, which is the optimum base, are used, the specific reaction temperature for n = 1 and 2 is usually 30 ° C., preferably 20 It is carried out at ° C, more preferably at 10 ° C. On the other hand, the lower limit is −50 ° C., preferably −20 ° C., more preferably 0 ° C. or higher.
The lower limit of the general reaction time in step (iii) is usually 30 minutes, preferably 60 minutes, more preferably 2 hours, and the upper limit is not particularly limited, but is usually 20 hours, preferably 10 hours, more preferably 5 hours. It's time.

<3.3.1.6 Separation and purification of target product>
After completion of the reaction, the target oligofluorene compound (II) can be isolated by adding the reaction liquid to acidic water such as dilute hydrochloric acid or adding acidic water such as dilute hydrochloric acid to the reaction liquid and precipitating. it can.
Moreover, after completion | finish of reaction, you may extract by adding the solvent and water in which the oligo fluorene compound (II) which is a target object is soluble to a reaction liquid. The target product extracted with a solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent. However, since the solubility of the oligofluorene compound (II) in a solvent tends to be very low at room temperature, a method of precipitation by contacting with acidic water is usually preferable.

The obtained oligofluorene compound (II) can be used as it is as a raw material in the step (iv), but may be used in the step (iv) after purification. As a purification method, usual purification methods such as recrystallization, reprecipitation method, extraction purification, column chromatography and the like can be employed without limitation.
On the other hand, the method for producing a difluorene compound in which the bridging group is other than a methylene group uses n-butyllithium as a base, and after generating anions of fluorenes (I), 1,2-diiodoethane, 1,3-diiodo Linear alkyl dihalides such as propane, 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane (excluding fluorine atoms) ), 1,4-bis (bromomethyl) benzene, aralkyl dihalides such as 1,3-bis (bromomethyl) benzene (excluding fluorine atoms), and the like, and methods for coupling with alkylating agents are widely known. A production method in which the group is an ethylene group or the crosslinking group is a propylene group is known (Organometrics, 200). , 27,3924; J.Molec.Cat.A:. Chem, 2004,214,187).. In addition to the alkylene group, there is a report example of crosslinking with a xylylene group (J. Am. Chem. Soc., 2007, 129, 8458.).

  However, industrially producing these methods using n-butyllithium tends to be very difficult both in terms of safety and cost. In addition, as a method for producing a difluorene compound, fluorene and diols such as ethylene glycol, propylene glycol, butylene glycol, pentylene glycol and hexylene glycol are heated at a high temperature (180 ° C.) in the presence of a base such as sodium hydroxide or potassium hydroxide. In the above, a method of dehydrating condensation is known (Patent Document 1, J. Org. Chem., 1965, 30, 2540.). However, since a reactor that uses a strong base and can withstand high-temperature conditions is required, there are many restrictions for industrialization.

On the other hand, the oligofluorene (2) having a carbon-carbon double bond of the present invention and the oligofluorene epoxy resin (1) of the present invention have a methylene group as a cross-linking group. It can be used to manufacture under mild conditions with few restrictions on industrialization.
<3.3.2 Step (iv): Production Method of Oligofluorene (2) Having Carbon-Carbon Double Bond by Alkylation of Oligofluorene Compound (II)>
In the presence of a base, oligofluorene (2) having a carbon-carbon double bond is abbreviated as oligofluorene compound (II) and an alkylating agent represented by the following general formula (IIIa) (hereinafter abbreviated as alkylating agent (IIIa)). And an alkylating reaction of an alkylating agent represented by the following general formula (IIIb) (hereinafter sometimes abbreviated as alkylating agent (IIIb)).

In formula, R < ¹ >, R < ² >, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). n shows the integer value of 1-5. X represents a leaving group. Examples of the leaving group include a halogen atom (excluding fluorine), a methanesulfonyloxy group, a p-toluenesulfonyloxy group, and the like.
Alkylation reactions of fluorenes are widely known. For example, 9,9-bis (haloalkyl) fluorene such as 9,9-bis (bromohexyl) fluorene and 9,9-bis (iodohexyl) fluorene (Reaction in a two-layer system: J. Org. Chem., 2010, 75, 2714., Reaction in a homogeneous system: Org. Lett., 2011, 13, 6429.). From these findings, it is possible to synthesize oligofluorene (2) having a carbon-carbon double bond by using oligofluorene (II) as a raw material.

<3.3.2.1 Alkylating agent>
Examples of the alkylating agents (IIIa) and (IIIb) used in the step (iv) include vinyl halides (excluding fluorine atoms) such as vinyl iodide, vinyl bromide and vinyl chloride, and allyl halides such as allyl iodide, allyl bromide and allyl chloride ( 2-alkylallyl halide such as 2-methylallyl iodide, 2-methylallyl bromide, 2-methylallyl chloride, 2-ethylallyl iodide, 2-ethylallyl bromide, 2-ethylallyl chloride, etc. (Excluding fluorine atoms), 4-iodo-1-butene, 4-bromo-1-butene, 4-chloro-1-butene, 5-iodo-1-pentene, 5-bromo-1-pentene, 5-chloro -1-pentene, 6-iodo-1-hexene, 6-bromo-1-hexene, B. Linear haloalkene such as 1-hexene (excluding fluorine atom), 4-bromo-2-methyl-1-butene, 5-bromo-2-ethyl-1-pentene, 6-bromo-2-ethyl Alkyl dihalides containing a branched chain such as -1-hexene and 6-chloro-2-methyl-1-hexene (excluding fluorine atoms), 4-vinylbenzyl chloride, 4-vinylbenzyl bromide, 3-vinylbenzyl chloride, Examples include vinyl benzyl halides such as 3-vinyl benzyl bromide, 2-vinyl benzyl chloride, 2-vinyl benzyl bromide, glycol sulfonates such as vinyl alcohol mesylate, allyl alcohol mesylate, vinyl alcohol tosylate, and allyl alcohol tosylate. It is done. These may be used alone or in combination of two or more.

  Among these, preferred are allyl halides such as allyl bromide and allyl chloride, and vinyl benzyl halides such as 4-vinylbenzyl chloride and 4-vinylbenzyl bromide, and more preferred are industrially available and inexpensive allyl bromides. , Allyl chloride. On the other hand, 4-vinylbenzyl chloride and 4-vinylbenzyl bromide are preferable from the viewpoint that a high glass transition temperature can be expected by having an aromatic ring.

  The amount of alkylating agents (IIIa) and (IIIb) used is not particularly limited with respect to the raw material oligofluorene compound (II), but if the amount used is too large, the purification load after the reaction tends to increase. Therefore, it is usually 10 times mol or less, preferably 6 times mol or less, more preferably 4 times mol or less of the oligofluorene compound (II). On the other hand, since there are two reactive sites with respect to one molecule of the oligofluorene compound (II), the lower limit is usually 2.0 times mol or more with respect to the raw material oligofluorene compound (II), preferably Is 2.2 times mole or more, more preferably 2.4 times mole or more.

<3.3.2.2 Base>
Examples of the base used in step (iv) include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide, and sodium carbonate. Alkali metal carbonates such as sodium hydrogen carbonate and potassium carbonate, alkaline earth metal carbonates such as magnesium carbonate and calcium carbonate, alkali metal salts of phosphoric acid such as sodium phosphate, sodium hydrogen phosphate and potassium phosphate, n
-Organolithium salts such as butyl lithium and tertiary butyl lithium, alkali metal alkoxide salts such as sodium methoxide, sodium ethoxide, potassium tertiary butoxide, alkali metal hydride salts such as sodium hydride and potassium hydride, Tertiary amines such as triethylamine and diazabicycloundecene, and quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetrabutylammonium hydroxide are used. These may be used alone or in combination of two or more.

  Since the oligofluorene compound (II) is easily decomposed by a reaction in a two-layer system, it is preferable to perform the reaction in a homogeneous system. Therefore, among the above bases, preferred are alkali metal alkoxides, and more preferred are sodium methoxide, sodium ethoxide and tert-butoxy potassium which are commercially available. Here, as the alkali metal alkoxide, a powdery one or a liquid one such as an alcohol solution may be used. Moreover, you may prepare by making an alkali metal and alcohol react.

  The amount of the base used is not particularly limited with respect to the raw material oligofluorene compound (II), but if the amount used is too large, the purification load after stirring and reaction becomes large. Therefore, the oligofluorene compound (II) is usually used. Is 10 times mol or less, preferably 6 times mol or less, more preferably 4 times mol or less. On the other hand, since there are two reactive sites with respect to one molecule of the oligofluorene compound (II), the lower limit is usually 2.0 times mol or more with respect to the raw material oligofluorene compound (II), preferably Is 2.2 times mole or more, more preferably 2.4 times mole or more.

<3.3.2.3 Solvent>
Step (iv) is preferably performed using a solvent. Specific examples of usable solvents include alkyl nitrile solvents such as acetonitrile and propionitrile, and ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane, methylcyclopentyl ether, and tertiary butyl methyl ether. As halogen solvents, 1,2-dichloroethane, dichloromethane, chloroform, 1,1,2,2-tetrachloroethane and the like, and as halogenated aromatic hydrocarbons, amides such as chlorobenzene and 1,2-dichlorobenzene, etc. Examples of the solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone. Examples of the sulfoxide solvent include dimethyl sulfoxide and sulfolane. Examples of the cyclic aliphatic hydrocarbon include cyclopenta. Monocyclic aliphatic hydrocarbons such as cyclohexane, cycloheptane and cyclooctane; derivatives thereof such as methylcyclopentane, ethylcyclopentane, methylcyclohexane, ethylcyclohexane, 1,2-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1,4-dimethylcyclohexane, isopropylcyclohexane, n-propylcyclohexane, tert-butylcyclohexane, n-butylcyclohexane, isobutylcyclohexane, 1,2,4-trimethylcyclohexane, 1,3,5-trimethylcyclohexane, etc .; Polycyclic aliphatic hydrocarbons; n-pentane, n-hexane, n-heptane, n-octane, isooctane, n-nonane, n-decane, n-dodecane, n-tetradecane, etc. Examples of acyclic aliphatic hydrocarbons and aromatic hydrocarbons include toluene, p-xylene, o-xylene, and m-xylene. Examples of alcohol solvents include methanol, ethanol, isopropanol, n-butanol, tertiary butanol, Examples include hexanol, octanol, and cyclohexanol.

Among them, an amide solvent or a sulfoxide solvent as a polar solvent is preferable because the solubility of anions generated from the oligofluorene compound (II) tends to be high and the reaction proceeds favorably. Among these, N, N-dimethylformamide is particularly preferable.
These solvents may be used alone or in combination of two or more.
If the amount of the solvent is too large, the productivity decreases and the load during purification increases, so the upper limit of the amount of solvent used is usually 10 times the volume of the raw material oligofluorene compound (II), preferably 7 The amount used is a double volume, more preferably a 4-fold volume. On the other hand, if the amount of the solvent used is too small, stirring becomes difficult and the progress of the reaction slows. Therefore, the lower limit is usually 1-fold volume, preferably 2-fold volume of the raw material oligofluorene compound (II). More preferably, the amount is 3 times the volume.

<3.3.2.4 Reaction format>
When carrying out step (iv), the type of reaction can be employed without any limitation, whether it is a batch type reaction, a flow type reaction or a combination thereof.

<3.3.2.5 Reaction conditions>
What is necessary is just to adjust process (iv) suitably according to the oligo fluorene (2) which has the target carbon-carbon double bond. If the temperature is too low, a sufficient reaction rate may not be obtained.
Therefore, the upper limit of the reaction temperature is usually 80 ° C., preferably 50 ° C., more preferably 40 ° C. On the other hand, the lower limit is usually -50 ° C, preferably -20 ° C, more preferably 0 ° C or higher.
The lower limit of the general reaction time in step (iv) is usually 30 minutes, preferably 60 minutes, more preferably 2 hours, and the upper limit is not particularly limited, but is usually 30 hours, preferably 20 hours, more preferably 10 hours. It's time.

<3.3.2.6 Separation and purification of target product>
After completion of the reaction, the target oligofluorene (2) having a carbon-carbon double bond is precipitated by adding the reaction solution to acidic water such as dilute hydrochloric acid or adding acidic water such as dilute hydrochloric acid to the reaction solution. Can be isolated.
Moreover, after completion | finish of reaction, you may extract by adding the solvent and water in which the oligo fluorene (2) which has the target carbon-carbon double bond is soluble to a reaction liquid. The target product extracted with a solvent can be isolated by a method of concentrating the solvent or a method of adding a poor solvent.

  The obtained oligofluorene (2) having a carbon-carbon double bond can be used as it is for the oxidation reaction as a raw material of the oligofluorene epoxy resin, but may be used for the oxidation reaction after purification. . In addition, oligofluorene (2) having a carbon-carbon double bond can be used as it is as a curable resin. As the purification method, a usual purification method such as recrystallization, reprecipitation method, extraction purification, column chromatography, etc. can be used without limitation.

<4 Oligofluorene epoxy resin derivative>
Derivatives can be obtained using the oligofluorene epoxy resin of the present invention. Specific derivatives include phenoxy resin (high molecular weight epoxy resin) reacted with an arbitrary amount of bisphenols, epoxy (meth) acrylate reacted with an arbitrary amount of (meth) acrylic acid, oligomer of epoxy resin, etc. Is mentioned.

<4.1 Phenoxy resin (high molecular weight epoxy resin)>
A phenoxy resin (high molecular weight epoxy resin) can be produced by reacting an oligofluorene epoxy resin with a bisphenol. The phenoxy resin can be cured either alone or mixed with any epoxy resin to impart toughness to the cured epoxy resin while maintaining the high refractive index and high transparency properties of the oligofluorene epoxy resin. can do.
Examples of the phenoxy resin reacted with an arbitrary amount of bisphenol include compounds represented by the following general formula (4).

In formula, R < ¹ >, R < ² >, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹⁴ is a divalent aromatic group. n represents an integer value of 1 to 5. m shows the numerical value of 0.1-100. ).
Here, examples of bisphenols used include bisphenol A, bispheno C, bisphenol F, bisphenol S, 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, Halogenated bisphenols such as tetrabromobisphenol A are exemplified. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

In the formula (4), as R ¹ and R ² , those exemplified for <1.3 substituents α ¹ and α ² > can be preferably used.
Similarly, as the alkyl group having 1 to 10 carbon atoms which may be substituted in R ¹⁰ , those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted with <1.2 epoxy group> And R ^{4 to} R ⁹ are preferably those exemplified in <1.4 Specific Structure>.
As R ¹⁴ , an aromatic group derived from bisphenols exemplified in <4.1 Phenoxy resin (high molecular weight epoxy resin)> can be preferably used.

<4.1.1 Physical Properties of Phenoxy Resin (High Molecular Weight Epoxy Resin)>
Although the physical property value of the phenoxy resin (high molecular weight epoxy resin) of this invention is not specifically limited, It is preferable that it satisfies the physical property value illustrated below.

The chlorine content in the phenoxy resin of the present invention is preferably 1000 mass ppm or less in terms of Cl. Furthermore, it is preferable that it is 100 mass ppm or less. When the content ratio of the chlorine component is large, the chlorine component remains in the obtained cured product, which may reduce the insulation of the cured product or corrode the metal wiring or the like that comes into contact.
The glass transition temperature of the phenoxy resin of the present invention is preferably 50 ° C. or higher. Furthermore, it is preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. When the phenoxy resin has a high glass transition temperature, it is possible to increase the heat resistance when the resin is cured.

The weight average molecular weight of the phenoxy resin of the present invention is preferably 1000 or more. Further, it is preferably 2000 or more, and particularly preferably 4000 or more. Moreover, as an upper limit, it is preferable that it is 100,000 or less. Further, it is preferably 50000 or less, and particularly preferably 30000 or less. Here, the weight average molecular weight is determined by a conversion value using standard polystyrene (method described in Examples described later). When the molecular weight is sufficiently large, a more flexible epoxy resin composition and cured product can be obtained.

<4.2 Epoxy (meth) acrylate>
Epoxy (meth) acrylate can be produced by reacting an oligofluorene epoxy resin with acrylic acid or methacrylic acid. In addition, an acylating agent may be reacted with a hydroxyl group generated by the reaction, or a bifunctional compound such as an acid dianhydride may be reacted to form an oligomer or a polymer. Good. The epoxy (meth) acrylate can be cured alone or mixed with any epoxy resin and any acrylate to cure and maintain the high refractive index and high transparency properties of the oligofluorene epoxy resin. A strong cured product can be obtained.
As an epoxy (meth) acrylate produced by including a step of reacting an oligofluorene epoxy resin with an arbitrary amount of (meth) acrylic acid, a compound represented by the following general formula (5) or the following general formula (6 ).

In formula, R < ¹ >, R < ² >, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a hydrogen atom or an acyl group. n shows the integer value of 1-5.

In formula, R < ¹ >, R < ² >, R < ⁴ > -R < ¹⁰ > is synonymous with the said General formula (1). R ¹² represents a hydrogen atom or a methyl group, and R ¹³ represents a hydrogen atom or an acyl group.
In the epoxy (meth) acrylate represented by the general formula (5) or the general formula (6), in order to produce an epoxy (meth) acrylate in which R ¹³ is an acyl group, an acylating agent or an acid diacid is used. Anhydrides are used.

  Specific examples of the acylating agent include monofunctional acylating agents such as acetic anhydride, acetyl chloride, propionic anhydride and benzoyl chloride; chloroformates such as ethyl chloroformate and allyl chloroformate; acrylic acid chloride, methacrylic acid chloride, (Meth) acrylic acids such as methacrylic anhydride; dodecenyl succinic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydroanhydride And cyclic acid anhydrides such as phthalic acid, methylcyclohexene dicarboxylic acid anhydride, phthalic anhydride, trimellitic anhydride, het acid anhydride, nadic anhydride, and methyl nadic anhydride.

Specific examples of the acid dianhydride include methylcyclohexene tetracarboxylic acid anhydride, pyromellitic anhydride, 4,4′-biphthalic acid anhydride, hydrogenated 4,4′-biphthalic acid anhydride, benzophenone tetracarboxylic acid Anhydride, ethylene glycol bis trimellitate dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3 , 4-tetrahydro-1-naphthalene succinic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the like.

  Of these acylating agents and acid dianhydrides, cyclic acid anhydrides and acid dianhydrides that can introduce carboxyl groups into the epoxy (meth) acrylate of the present invention are preferred. The epoxy (meth) acrylate having a carboxyl group introduced therein can be dissolved and removed by basic water in an uncured state, and therefore can be used as a negative resist material. In particular, acid dianhydrides are preferred, and oligomer and polymer epoxy (meth) acrylates having suitable viscosity and number of functional groups as a resist material can be obtained.

In the formulas (5) and (6), as R ¹ and R ² , those exemplified for <1.3 substituents α ¹ and α ² > can be preferably used.
Similarly, as the alkyl group having 1 to 10 carbon atoms which may be substituted in R ¹⁰ , those exemplified as the alkyl group having 1 to 10 carbon atoms which may be substituted with <1.2 epoxy group> And R ^{4 to} R ⁹ are preferably those exemplified in <1.4 Specific Structure>.
R ¹² and R ¹³ are preferably hydrogen atoms.

<4.2.1 Physical properties of epoxy (meth) acrylate>
Although the physical property value of the epoxy (meth) acrylate of this invention is not specifically limited, It is preferable that the physical property value illustrated below is satisfied.
The chlorine content in the epoxy (meth) acrylate of the present invention is preferably 1000 ppm by mass or less in terms of Cl. Furthermore, it is preferable that it is 100 mass ppm or less. When the content ratio of the chlorine component is large, the chlorine component remains in the obtained cured product, which may reduce the insulation of the cured product or corrode the metal wiring or the like that comes into contact.

  The melting point of the epoxy (meth) acrylate of the present invention is preferably 150 ° C. or less. Furthermore, it is preferable that it is 100 degrees C or less, and it is especially preferable that it is 50 degrees C or less. When curing the composition, it is usually necessary to heat and melt and mix. However, if the melting point is high, the melting temperature becomes high and the operability deteriorates, and the curing starts before mixing and the quality is stable and uniform. Difficult to obtain a cured product.

  It is preferable that the 150 degreeC melt viscosity of the epoxy (meth) acrylate of this invention is 10 P or less. Furthermore, it is preferably 4P or less, and particularly preferably 1P or less. When the viscosity is low, mixing of the composition by heating and melting becomes easy, and moldability and workability are improved. Furthermore, it becomes possible to add more fillers, and the physical properties of the cured product can be adjusted.

The refractive index at 589 nm of the epoxy (meth) acrylate of the present invention is preferably 1.58 or more, and more preferably 1.60 or more. Further, it is preferably 1.62 or more, and particularly preferably 1.63 or more. Here, the refractive index is obtained by an extrapolation method of DMF solution (method described in Examples described later) assuming that the specific gravity of the epoxy (meth) acrylate of the present invention is 1.2. Since the refractive index is high, it can be made thin and light when used in an optical material such as a lens, and a material having a wide range of refractive index can be obtained by mixing with other materials.

<5. Oligofluorene epoxy resin composition>
An epoxy resin composition means the whole mixture containing an epoxy resin, which is a raw material for organic and inorganic substances contained in the cured product when it is made into a cured product. The epoxy resin means a simple substance or a mixture of compounds containing an epoxy group as a functional group. The oligofluorene epoxy resin composition of the present invention contains the above-described oligofluorene epoxy resin of the present invention. In addition to the oligofluorene epoxy resin, (A) another epoxy resin, (B) a curing agent, (C ) Filler, (D) Other various additives may be included.

In addition, the oligofluorene having a carbon-carbon double bond of the present invention and the epoxy (meth) acrylate compound of the present invention are also similar to the epoxy resin composition of the present invention in (A) other epoxy resins, (B) It can be set as the composition containing a hardening | curing agent, (C) filler, (D) other various additives. In addition, (E) you may use together with the compound which has another carbon-carbon double bond.
Here, the oligofluorene epoxy resin composition of the present invention, the oligofluorene composition having a carbon-carbon double bond of the present invention, and the epoxy (meth) acrylate compound composition of the present invention are collectively referred to as an epoxy resin composition. Call a thing.

<5.1 (A) Other epoxy resin>
In the epoxy resin composition of the present invention, as the epoxy resin, the oligofluorene epoxy resin of the present invention may be used alone or in combination with other epoxy resins. When using together, the ratio of the epoxy resin of this invention in all the epoxy resin components (total amount of the epoxy resin of this invention and another epoxy resin) can be set arbitrarily.

Other epoxy resins that can be used in combination with the epoxy compound of the present invention, or other epoxy resins that can be used in the composition of the epoxy resin of the present invention include, for example, novolac type epoxy resins, bisphenol A type epoxy resins, and biphenyl type epoxy resins. , Triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin and the like.
Specifically, for example, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl -(1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane , Phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetate Enone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc., and their modified products, halogenated bisphenols such as tetrabromobisphenol A, or alcohols Glycidyl etherified product of alicyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or a mixture of at least two of them) Siloxane structure with glycidyl group and / or epoxycyclohexa Include solid or liquid epoxy resin having an epoxy resin) having the structure. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

In particular, when the composition of the present invention, such as an epoxy resin, is used for optical applications, it is preferably used in combination with an alicyclic epoxy resin or an epoxy resin having a silsesquioxane structure. In particular, in the case of an alicyclic epoxy resin, a compound having an epoxycyclohexane structure in the skeleton is preferable, and an epoxy resin obtained by an oxidation reaction of a compound having a cyclohexene structure is preferable.
Specific examples of these epoxy resins include, for example, ERL-4221 and UVR-6105.
ERL-4299 (all trade names, all manufactured by Dow Chemical Co.), Celoxide 2021P, Eporide GT401, EHPE3150, EHPE3150CE (all trade names, all manufactured by Daicel Chemical Industries) and dicyclopentadiene diepoxide. However, it is not limited to these (references: review epoxy resin basics edition I p76-85). These may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, when the oligofluorene epoxy resin of the present invention and another epoxy resin are used, the blending amount of the oligofluorene epoxy resin of the present invention in all epoxy resins is usually 10 to 100% by mass, Preferably it is 20-95 mass%, Most preferably, it is 40-90 mass%. When the ratio of the epoxy resin of the present invention is equal to or higher than the lower limit value, it is possible to sufficiently obtain the improvement effect of the refractive index, workability, heat resistance, etc. by blending the epoxy resin of the present invention, the upper limit value. By being below, various effects which other epoxy resins have, such as processability control and physical property control of hardened | cured material, can fully be acquired.

<5.1.1 (A ') Compound in which epoxy group is partially substituted with carbon-carbon double bond>
The oligofluorene epoxy resin composition of the present invention is a compound in which one of two epoxy rings is substituted with a carbon-carbon double bond instead of an epoxy ring (hereinafter referred to as (A ′ ) May be abbreviated as a compound in which an epoxy group is partially substituted with a carbon-carbon double bond. (A ′) The compound in which an epoxy group is partially substituted with a carbon-carbon double bond is used to control the amount of an oxidizing agent when an oligofluorene epoxy resin is produced by oxidation of oligofluorene having a carbon-carbon double bond. Can be manufactured. The oligofluorene epoxy resin composition of the present invention preferably contains (A ′) a compound in which an epoxy group is partially substituted with a carbon-carbon double bond, thereby lowering the melting point and viscosity and improving workability. .

  (A ') The compound in which the epoxy group is partially substituted with a carbon-carbon double bond is specifically represented by the following general formula (3). Although it does not specifically limit as a carbon-carbon double bond, You may have a C1-C10 alkyl group which may be substituted.

Wherein, R ^1, R ^2, and R ⁴ to R ¹⁰ are as defined in the general formula (1). n shows the integer value of 1-5.
In the oligofluorene epoxy resin composition of the present invention, since the melting point is lowered and the viscosity can be lowered by including a compound in which (A ′) an epoxy group is partially substituted with a carbon-carbon double bond, processability is improved. From the viewpoint, it is preferable to contain a compound in which an epoxy group is partially substituted with a carbon-carbon double bond, and the content thereof is preferably 0.1% by mass or more, more preferably 1% by mass or more, and still more preferably. When the content is 5% by mass or more and the content is large, curing failure, a decrease in the glass transition point, and the like are caused.

  (A ′) Specific examples of the compound in which the epoxy group is partially substituted with a carbon-carbon double bond include structures as shown in the following [K] group.

<5.2 (B) Hardener>
The composition such as an epoxy resin in the present invention may contain (B) a curing agent. The hardening | curing agent which can be used for compositions, such as an epoxy resin of this invention, shows the substance which contributes to the crosslinking reaction of the epoxy group of an epoxy resin. There is no restriction | limiting in particular as a hardening | curing agent used for this invention, Generally what is known as an epoxy resin hardening | curing agent can be used. For example, phenolic curing agents, primary and secondary amine curing agents, addition polymerization curing agents such as acid anhydride curing agents, tertiary amine curing agents, imidazole curing agents, organic phosphine curing agents, Examples thereof include catalytic curing agents such as phosphonium salt curing agents and cationic polymerization initiators.

  Moreover, as a hardening | curing agent which can be used for compositions, such as an epoxy resin of this invention, the substance which contributes to the crosslinking reaction of a carbon-carbon double bond and the carbon-carbon double bond of (meth) acrylate should be used similarly. Can do. There is no restriction | limiting in particular as a hardening | curing agent used for this invention, Generally what is known as a carbon-carbon double bond and a (meth) acrylate hardening | curing agent can be used. Examples thereof include addition polymerization type curing agents such as thiol type curing agents and silane type curing agents, and catalyst type curing agents such as metal catalysts and radical polymerization initiators.

  Specific examples of the phenolic curing agent include bisphenol A, bisphenol F, 4,4′-dihydroxydiphenylmethane, 4,4′-dihydroxydiphenyl ether, 1,4-bis (4-hydroxyphenoxy) benzene, 1,3- Bis (4-hydroxyphenoxy) benzene, 4,4′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl sulfone, 4,4′-dihydroxybiphenyl, 2,2′-dihydroxy Biphenyl, 10- (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, phenol novolak, bisphenol A novolak, o-cresol novolak, m-cresol novolak, p- Resole novolak, xylenol novolak, poly-p-hydroxystyrene, hydroquinone, resorcin, catechol, t-butylcatechol, t-butylhydroquinone, fluoroglycinol, pyrogallol, t-butyl pyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1, 2,4-benzenetriol, 2,3,4-trihydroxybenzophenone, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxy Naphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, , 6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,8-dihydroxynaphthalene, allylated or polyallylated products of the above-mentioned dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, allylated phenol novolak, allylated pyrogallol, etc. Can be mentioned.

Examples of the primary and secondary amine curing agents include aliphatic amines, polyether amines, alicyclic amines, aromatic amines and the like. Aliphatic amines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminopropane, hexamethylenediamine, 2,5-dimethylhexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, iminobispropylamine, bis ( Hexamethylene) triamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, N-hydroxyethylethylenediamine, tetra (hydroxyethyl) ethylenediamine and the like. Examples of polyether amines include triethylene glycol diamine, tetraethylene glycol diamine, diethylene glycol bis (propylamine), polyoxypropylene diamine, and polyoxypropylene triamines. Cycloaliphatic amines include isophorone diamine, metacene diamine, N-aminoethylpiperazine, bis (4-amino-3-methyldicyclohexyl) methane, bis (aminomethyl) cyclohexane, 3,9-bis (3-amino). Propyl) -2,4,8,10-tetraoxaspiro [5.5] undecane, norbornenediamine and the like. Aromatic amines include tetrachloro-p-xylenediamine, m-xylenediamine, p-xylenediamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 2,4-diaminoanisole, 2,4 -Toluenediamine, 2,4-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane, 2,4-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, m-aminophenol, m-aminobenzylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, triethanolamine, methylbenzylamine, α- (3-aminophenyl) ethylamine, α- (4-aminophenyl) Ethylamine, diaminodiethyl Examples thereof include dimethyldiphenylmethane and α, α′-bis (4-aminophenyl) -p-diisopropylbenzene.

  Specific examples of the acid anhydride curing agent include dodecenyl succinic anhydride, polyadipic acid anhydride, polyazeline acid anhydride, polysebacic acid anhydride, poly (ethyloctadecanedioic acid) anhydride, poly (phenylhexadecanedioic acid). ) Anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylhymic anhydride, tetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, methylcyclohexenedicarboxylic anhydride, methylcyclohexenetetra Carboxylic anhydride, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, 4,4'-biphthalic anhydride, hydrogenated 4,4'-biphthalic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol Bistrimellitate 2 , Anhydrous hectic acid, nadic anhydride, methyl nadic anhydride, 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexane-1,2-dicarboxylic anhydride, 3, 4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1-methyl-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and the like.

Examples of the tertiary amine-based curing agent that can be used as the curing agent include 1,8-diazabicyclo [5.4.0] -7-undecene, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris. (Dimethylaminomethyl) phenol and the like can be mentioned.
Examples of the imidazole-based curing agent that can be used as the curing agent include 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl- 2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyano-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6- (2-methyl-1-imidazolyl) -ethyl-s-triazine, 2,4-diamino-6- (2-ethyl-4-methyl-1-imidazolyl) -ethyl-s- Triazine, 2,4-diamino-6- (2-methyl-1-imidazolyl)- Tyr-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, and epoxy resin and the above Examples include adducts with imidazoles.

  Examples of the organic phosphine curing agent that can be used as a curing agent include tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine. Phosphonium salt curing agents include tetraphenylphosphonium tetra Examples thereof include phenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, methyltributylphosphonium / dimethylphosphate (PX-4MP) and the like.

Examples of the cationic polymerization initiator include those having an onium salt such as an iodonium salt, a sulfonium salt, or a diazonium salt. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.
Examples of the photocationic polymerization initiator include metal fluoroboron complex salts and boron trifluoride complex compounds (US Pat. No. 3,379,653), bis (perfluoroalkylsulfonyl) methane metal salts (US Pat. No. 3,586,616). An aryldiazonium compound (US Pat. No. 3,708,296), an aromatic onium salt of a VIa group element (US Pat. No. 4,058,400), an aromatic onium salt of a Group Va element (US Pat. No. 4069055), Dicarbonyl chelates of group IIIa-Va elements (US Pat. No. 4068091), thiopyrylium salts (US Pat. No. 4,139,655), group VIb elements in the form of MF6-anions (US Pat. No. 4,161,478); M is selected from phosphorus, antimony and arsenic.), Ants Rusulfonium complex salts (US Pat. No. 4,231,951), aromatic iodonium complex salts and aromatic sulfonium complex salts (US Pat. No. 4,256,828), and bis [4- (diphenylsulfonio) phenyl] sulfide-bis-hexafluoro Metal salts (Journal of Polymer Science, Polymer Chemistry, Volume 2,
1789 (1984)). In addition, mixed ligand metal salts of iron compounds and silanol-aluminum complexes can also be used.

Specific examples include “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” (manufactured by General Electronics Co., Ltd.), and “CD-1012” (Sartomer Company). Product), “RP-2074” (manufactured by Rhodia), and the like.
Furthermore, these photocationic polymerization initiators, known polymerization initiation assistants, and photosensitizers may be used alone or in combination of two or more in any combination.

  Examples of the polymerization initiation auxiliary agent include benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2- Methyl-1- (4-methylthiophenyl) -2-morpholinolpropan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone 2-amylanthraquinone, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl Ketal, benzophenone, 4-methylbenzophenone, 4,4'-dichlorobenzophenone, 4,4'-bis-diethylamino benzophenone, and a photo-radical polymerization initiator such as Michler's ketone.

The amount of the polymerization initiation auxiliary agent such as a photo radical polymerization initiator is usually 0.01 parts by mass or more, preferably 0.1 parts by mass or more, and usually 100 parts by mass with respect to 100 parts by mass of the photo radical capable component. 30 parts by mass or less, preferably 10 parts by mass or less.
Examples of the photosensitizer include anthracene, 2-isopropylthioxatone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acridine orange, acridine yellow, phosphine R, and benzoflavine. , Cetoflavin T, perylene, N, N-dimethylaminobenzoic acid ethyl ester, N, N-dimethylaminobenzoic acid isoamyl ester, triethanolamine, triethylamine and the like.

The amount of the photosensitizer used is usually 0.01 or more, preferably 0.1 or more, and usually 30 or less, preferably 10 parts by mass with respect to 100 parts by mass of all epoxy resin components. It is as follows.
Specific examples of the thiol-based curing agent include, for example, trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylolpropane tris (β-thiopropionate). Thiol compounds obtained by esterification of polyols such as pentaerythritol tetrakis (β-thiopropionate) and dipentaerythritol poly (β-thiopropionate) with mercapto organic acids; 1,4-butanedithiol, 1 Alkylpolythiol compounds such as 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, 1,10-decanedithiol; terminal thiol group-containing polyether; Thiol compounds having a terminal thiol group obtained by reaction of a polythiol compound and an epoxy compound; Le-containing polythioether; thiol compounds obtained by the reaction of an epoxy compound with hydrogen sulfide, and the like.

Specific examples of the silane curing agent include polymethylsiloxane having a hydrosilyl group, polymethylphenylsiloxane, polyphenylsiloxane, polyethylsiloxane, and polyoctylmethylsiloxane. The polysiloxane may be any of a chain, a ring, a branch, and a three-dimensional network.
Specific examples of the metal catalyst include a platinum-based catalyst that catalyzes a hydrosilylation reaction, a metathesis catalyst that reacts with a carbon-carbon double bond, and the like.

  The platinum-based catalyst may be a known catalyst containing one or more metals of platinum, palladium and rhodium that promote the hydrosilylation reaction. Examples of the platinum-based catalyst used as a catalyst for these hydrosilylation reactions include a platinum-carbonylvinylmethyl complex, a platinum-divinyltetramethyldisiloxane complex, a platinum-cyclovinylmethylsiloxane complex, and a platinum-octylaldehyde complex. In addition to platinum-based catalysts, compounds containing platinum, rhodium, etc., which are also platinum-based metals, can be used, and one or more of these may be used in combination. In particular, those containing platinum are preferred from the viewpoint of curability, and specifically, platinum-divinyltetramethyldisiloxane complex and platinum-carbonylvinylmethyl complex are preferred.

  As the metathesis catalyst, atoms of Group 5, Group 6, and Group 8 (long period periodic table, the same applies hereinafter) are used as transition metal atoms. The atoms of each group are not particularly limited, but the preferred Group 5 atom is tantalum, the preferred Group 6 atom is molybdenum and tungsten, and the preferred Group 8 atom is ruthenium and osmium. A particularly preferred metathesis polymerization catalyst is a ruthenium carbene complex.

The amount of the metal catalyst used is preferably 5 parts by mass or less, more preferably 0.0001 to 1.0 part by mass with respect to 100 parts by mass of the epoxy resin or the like in the composition such as an epoxy resin from the viewpoint of reactivity.
Specific examples of the radical polymerization initiator include a photo radical polymerization initiator and a thermal polymerization initiator.

Examples of the photo radical polymerization initiator include acetophenone, anthraquinone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, carbazole, xanthone, 4-chlorobenzophenone, 4,4′- Diaminobenzophenone, 1,1-dimethoxydeoxybenzoin, 3,3′-dimethyl-4-methoxybenzophenone, thioxanthone compound, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-2- ON, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, triphenylamine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxy) Benzoyl) -2,4,4-tri-methylpen Ruphosphine oxide, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, fluorenone, fluorene, benzaldehyde, benzoin ethyl ether, benzoin propyl ether, benzophenone, Michler's ketone, 3
-Methylacetophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone (BTTB) and the like.

  Examples of the thermal polymerization initiator include dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; dialkanoyl peroxide such as lauroyl peroxide; benzoyl peroxide, benzoyl toluyl peroxide, and toluyl peroxide Peracid esters such as percarboxylic acid alkyl esters such as t-butyl peracetate, t-butyl peroxyoctoate and t-butylperoxybenzoate; ketone peroxides, peroxycarbonates Organic peroxides such as peroxyketals; 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2- Methylbutyronitrile), 2 Azonitrile compounds such as 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl Azoamide compounds of propionamide; azoamidine compounds such as 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride Azoalkane compounds such as 2,2′-azobis (2,4,4-trimethylpentane) and 4,4′-azobis (4-cyanopentanoic acid); 2,2′-azobis (2-methylpropionamide oxime, etc. And azo compounds having an oxime skeleton.

A radical photopolymerization initiator and a thermal polymerization initiator may be used alone or in combination of two or more kinds, or a radical radical polymerization initiator and a thermal polymerization initiator may be used in combination of two or more kinds.
The curing agents listed above may be used alone or in a combination of two or more in any combination and ratio. When the curing agent is an addition polymerization type curing agent, it reacts with a reactive functional group such as an epoxy group in a composition such as an epoxy resin and a reactive functional group such as an epoxy group in the curing agent to form a crosslinked structure. It is preferable to use it so that it may become the range of 0.8-1.5 by an equivalent ratio with the reaction site to perform, and it is more preferable to use so that it may become the range of 0.9-1.2. If it is outside this range, reactive functional groups such as unreacted epoxy groups and reaction sites of the curing agent may remain, and desired physical properties may not be obtained. On the other hand, when the curing agent is a catalyst-type curing agent, unless otherwise specified in the specific example of the curing agent, 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin or the like in the composition such as an epoxy resin. Is preferably used in the range of 0.2 to 10 parts by mass. If the amount of the curing agent is too small, sufficient curing cannot be achieved, and if the amount is too large, the effect of the curing agent on the resin cured product tends to increase and the properties of the resin cured product tend to deteriorate.
In addition, which of these curing agents is used is variously selected according to the balance of various properties such as curing conditions and the shape of the cured resin, the heat resistance, adhesiveness, water absorption, and bending strength of the cured resin. .

<5.3 (C) Filler>
The composition such as an epoxy resin of the present invention may contain (C) a filler. By including the filler, it is possible to improve various properties such as improvement of the thermal conductivity of the resin cured product and reduction of the linear expansion coefficient.
As fillers, insulating fillers such as alumina, aluminum nitride, boron nitride, silicon nitride, silica, zircon, calcium silicate, calcium carbonate, magnesium oxide, zirconia, fosterite, steatite, spinel, titania, talc, Examples include electrically conductive fillers such as aluminum, silver, copper, carbon, and silicon carbide. Among these, it is preferable to use an insulating filler in order to impart insulating properties to the cured resin. Furthermore, it is preferable to use alumina, aluminum nitride, boron nitride, or silica as a filler from the viewpoint of obtaining an inexpensive composition such as an epoxy resin, and particularly from the viewpoint of improving thermal conductivity, alumina, aluminum nitride, or nitriding. Boron is preferred, and silica is preferred for the purpose of increasing the filling amount and lowering the linear expansion coefficient. These fillers may be used alone or in a combination of two or more in any combination and ratio.

  In addition, the shape of the filler is not particularly limited, but when using a filler having a small surface area such as a spherical shape, there is a tendency to improve workability, and when using a filler having a large surface area such as a fibrous form, There is a tendency to make various properties such as the thermal conductivity of the filler more easily exhibited in the cured product, and when using an intermediate surface such as a flat shape, it is easy to balance the two There is.

  If the particle size is too large, voids are likely to remain in the cured product. If the particle size is too small, the filler is likely to aggregate and deteriorate dispersibility. Therefore, a filler having an average particle size of about 0.01 to 1000 μm is used. It is preferable. For the purpose of increasing the filling amount and lowering the linear expansion coefficient, it is more preferable to use a material having a thickness of about 0.1 to 200 μm, and it is particularly preferable to use a material having a thickness of 0.5 to 100 μm. For the purpose of reducing the linear expansion coefficient while maintaining transparency, it is more preferable to use a material having a thickness of about 0.01 to 1 μm, and it is particularly preferable to use a material having a thickness of 0.05 to 0.2 μm. The average particle diameter can be obtained from the result of measuring the volume distribution by an existing measuring method such as laser diffraction / scattering method or sedimentation method.

  When the composition such as an epoxy resin of the present invention contains a filler, the blending ratio of the filler is preferably 10 to 95% by mass, more preferably 20 to 90% by mass with respect to the composition such as the epoxy resin. When the blending amount of the filler is equal to or higher than the lower limit value, a sufficient blending effect of the filler is exhibited, and when it is equal to or lower than the upper limit value, sufficient workability of the composition such as an epoxy resin is obtained. There is a tendency to be able to.

<5.4 (D) Other additives>
The composition such as an epoxy resin of the present invention may contain various additives for the purpose of further improving its functionality. Examples of such other additives include flame retardants for imparting flame retardancy (phosphorus-containing compounds such as flame retardants), antioxidants for preventing yellowing due to oxidation, and deterioration (phenolic antioxidants). , Sulfur-based antioxidants, phosphorus-based antioxidants), silane coupling agents, titanate coupling agents, etc. as additive components to improve adhesion to substrates and adhesion between matrix resins and inorganic fillers Coupling agent, phosphor, UV protection agent for improving storage stability, plasticizer, flux for removal of solder oxide film, colorant, dispersant, emulsifier, low elasticity agent, diluent, antifoam Agents, ion trapping agents and the like.

Furthermore, other resin can be mix | blended with the resin etc. composition of this invention as needed.
The phosphorus-containing compound that can be contained in the composition such as the epoxy resin of the present invention may be a reactive type or an additive type. Specifically, for example, trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis (dixylyl) Phosphoric esters such as lenyl phosphate), 1,4-phenylenebis (dixylenyl phosphate), 4,4′-biphenyl (dixylyl phosphate); 9,10-dihydro-9-oxa-10 A phosphane such as phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; an epoxy resin and active hydrogen of the phosphane Phosphorus-containing epoxy compound obtained by reaction , Red phosphorus and the like. Among these, phosphoric acid esters, phosphanes, and phosphorus-containing epoxy compounds are preferable. More specifically, 1,3-phenylenebis (dixylylenyl phosphate) and 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.

Content of a phosphorus containing compound is mass ratio with respect to all the epoxy resins, Preferably it is 0.1 or more and 0.6 or less. When the content (mass ratio) is 0.1 or less, the flame retardancy is insufficient, and when it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.
Furthermore, you may add antioxidant to compositions, such as an epoxy resin of this invention, as needed. Examples of the antioxidant that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. The usage-amount of antioxidant is 0.008 mass part or more normally with respect to 100 mass parts of resin components in a resin composition, Preferably it is 0.01 mass part or more, Usually 1 mass part or less, Preferably it is 0. .5 parts by mass or less.

  Examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate and the like; 2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl- 6-t-butylphenol), 4,4′-thiobis (3-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 3,9-bis [1 , 1-Dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxa Bisphenols such as spiro [5.5] undecane; 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2,4,6 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, bis [3 3-bis- (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -s-triazine Polymeric phenols such as 2,4,6- (1H, 3H, 5H) trione and tocophenol are exemplified.

Examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate.
Examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. ; 9,10-dihydride -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene- Examples thereof include oxaphosphaphenanthrene oxides such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and the like.

These antioxidants may be used individually by 1 type, and may use 2 or more types together by arbitrary combinations. In the present invention, a phosphorus-based antioxidant is particularly preferable.
Furthermore, a light stabilizer can be added to the composition of the present invention such as an epoxy resin, if necessary.
As the light stabilizer, a hindered amine light stabilizer (hereinafter sometimes referred to as “HALS”) is suitable. Examples of HALS include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine and N- ( 2,2,6,6-tetramethyl-4-piperidyl) butylamine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2 , 4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6 , 6-Tetramethyl-4-piperidyl ) Sebacate etc. These may be used alone or in combination of two or more in any combination.

  Examples of silane coupling agents include epoxy silanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-aminopropyl. Triethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, etc. Aminosilane, mercaptosilane such as 3-mercaptopropyltrimethoxysilane, p-styryltrimethoxysilane, vinyltrichlorosilane, vinyltris (8-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, γ- Examples include vinyl silanes such as methacryloxypropyltrimethoxysilane, and epoxy-type, amino-type, and vinyl-type polymer silanes.

  On the other hand, titanate coupling agents include isopropyl triisostearoyl titanate, isopropyl tri (N-aminoethyl / aminoethyl) titanate, diisopropyl bis (dioctyl phosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis ( Ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate It is done.

  In addition, it is preferable that the addition amount of a coupling agent shall be about 0.1-2.0 mass% with respect to the total solid in compositions, such as an epoxy resin, among other additives. If the amount of the coupling agent is small, the effect of improving the adhesion between the matrix resin and the inorganic filler due to the incorporation of the coupling agent cannot be obtained sufficiently. The agent may bleed out. The coupling agents represented by the silane coupling agents and titanate coupling agents mentioned above may be used alone or in combination of two or more in any combination and ratio. . Moreover, there is no restriction | limiting in particular in the compounding quantity of another additive, It is used with the compounding quantity of a normal resin composition to such an extent that required functionality is obtained.

  When the composition such as the epoxy resin of the present invention is used for an optical semiconductor sealing material, a phosphor can be added as necessary. For example, the phosphor has a function of forming white light by absorbing part of blue light emitted from a blue LED element and emitting wavelength-converted yellow light. After the phosphor is dispersed in advance in a composition such as an epoxy resin, the optical semiconductor is sealed. There is no restriction | limiting in particular as fluorescent substance, A conventionally well-known fluorescent substance can be used.

Examples of other resins include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, silicone resins, and the like. Is mentioned. These may be used individually by 1 type and may use 2 or more types together by arbitrary combinations.
The blending amount of the other resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 parts by mass or more with respect to 100 parts by mass of the epoxy resin or the like composition. The amount is usually 50 parts by mass or less, preferably 20 parts by mass or less.

<5.5 Solvent>
The composition such as an epoxy resin of the present invention may contain a solvent in order to appropriately adjust the viscosity during processing. Examples of the solvent that the epoxy resin composition of the present invention can contain include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, esters such as ethyl acetate, ethers such as ethylene glycol monomethyl ether, N, N- Examples thereof include amides such as dimethylformamide and N, N-dimethylacetamide, alcohols such as methanol and ethanol, alkanes such as hexane and cyclohexane, and aromatics such as toluene and xylene.

The solvent mentioned above may be used only by 1 type, and may mix and use 2 or more types by arbitrary combinations and a ratio. Further, in the epoxy resin composition containing the epoxy resin of the present invention, as described above, the solvent is used to ensure the handling property and workability in the molding of the epoxy resin composition, etc. There is no limit.
In addition, it is preferable not to use a solvent for a composition, such as an epoxy resin in this invention, from a viewpoint of preventing the void formation by a solvent remaining at the time of hardening.

<5.6 (E) Compound having other carbon-carbon double bond>
The composition such as an epoxy resin of the present invention can be used in combination with another compound having a carbon-carbon double bond. When used in combination, the ratio of the composition such as the epoxy resin of the present invention in all components (the total amount of the composition such as the epoxy resin of the present invention and the other compound having a carbon-carbon double bond) is arbitrarily set. be able to.

The compounds having other carbon-carbon double bonds that can be used in combination with the composition such as the epoxy resin of the present invention can be roughly classified into (meth) acrylic compounds and non- (meth) acrylic compounds. Although it does not specifically limit as a (meth) acrylic-type compound, For example, it can divide roughly into a monofunctional compound and a polyfunctional compound.
Specific examples of monofunctional (meth) acrylic compounds include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, and butyl (meth) acrylate; (meth) acrylic acid (Meth) acrylate cycloalkyl such as cyclohexyl; (meth) acrylate polycyclic cycloalkyl such as bornyl (meth) acrylate and isobornyl (meth) acrylate; aryl (meth) acrylate such as phenyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate; diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate Any (poly) oxyalkylene glycol mono (meth) acrylate; alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate; trifluoroethyl (meth) acrylate, tetra Haloalkyl (meth) acrylates such as fluoropropyl (meth) acrylate and hexafluoroisopropyl (meth) acrylate; Aryloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylate; Aminoalkyl such as N, N-dimethylaminoethyl acrylate (Meth) acrylates; (Meth) such as glycidyl (meth) acrylate and tetrahydrofurfuryl (meth) acrylate
(Meth) acrylic acid; (meth) acrylamide; N-substituted (meth) acrylamide such as N, N-dimethyl (meth) acrylamide; (meth) acrylamides such as N-methylol (meth) acrylamide Can be mentioned. Monofunctional (meth) acrylic compounds may be used alone or in combination of two or more.

Among these, preferable monofunctional (meth) acrylic compounds include (meth) acrylic acid alkyl esters. In particular, methyl (meth) acrylate and ethyl (meth) acrylate are more preferable because they can be obtained industrially at low cost.
The polyfunctional (meth) acrylic compound is classified into a bifunctional (meth) acrylic compound and a trifunctional or higher (meth) acrylic compound.

  Bifunctional (meth) acrylic compounds include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, hexanediol di (meth) acrylate, neo Alkylene glycol di (meth) acrylates such as pentyl glycol di (meth) acrylate; diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, Polyoxymethylene glycol di (meth) acrylate such as polytetramethylene glycol di (meth) acrylate; di (meth) acrylate of bisphenol A; glycerin di (meth) acrylate Lilate, trimethylolpropane di (meth) acrylate, tris (di (meth) acrylate of triol such as hydroxyethyl isocyanurate di (meth) acrylate); di (meth) acrylate of tetraol such as pentaerythritol di (meth) acrylate; Examples include bridged cyclic (meth) acrylates such as tricyclodecane dimethanol di (meth) acrylate.

  Trifunctional or higher (meth) acrylic compounds include glycerin tri (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra Polyfunctional (meth) such as (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate etc. Acrylate and the like are included.

Polyfunctional (meth) acrylic compounds may be used alone or in combination of two or more.
Specific examples of non- (meth) acrylic compounds include chain olefins such as ethylene, propylene, 1-butene, butadiene, and isoprene; cyclic olefins such as norbornene, pinene, cyclopentadiene, cyclopentadiene, and dicyclopentadiene; styrene , Α-methylstyrene, vinyltoluene, divinylbenzene, vinylnaphthalene and other styrene compounds; vinyl acetate compounds such as vinyl acetate; nitrogen-containing compounds such as vinylpyrrolidone and triallyl isocyanurate; halogens such as vinyl chloride and chloroprene Vinyl cyanide compounds such as (meth) acrylonitrile; alkyl vinyl ethers such as methyl vinyl ether; (anhydrous) maleic acid, fumaric acid, itaconic acid, N-phenylmaleimide, 1,3 Phenylene bismaleimide, 1,4-phenylene bismaleimide, unsaturated carboxylic acid-based compounds such as 4,4'-diphenylmethane bismaleimide; and the like. These non- (meth) acrylic compounds may be used alone or in combination of two or more.

<6. Cured product>
The cured product of the present invention is obtained by curing the composition such as the epoxy resin of the present invention.
The cured product obtained by curing the composition such as the epoxy resin of the present invention exhibits high cured properties such as high transparency, refractive index and heat resistance, and is useful for various applications described below.

[Usage]
The cured product obtained by curing the composition such as the epoxy resin of the present invention, particularly the cured product obtained by curing the oligofluorene epoxy resin composition of the present invention, can be suitably used for optical materials, electronic materials and the like. it can.

[Physical properties of cured product]
The chlorine content in the cured product of the present invention is usually 1000 ppm by mass or less in terms of Cl, preferably 500 ppm by mass or less, more preferably 300 ppm by mass or less, more preferably 100 ppm by mass or less, and still more preferably. It is preferably 50 ppm by mass or less, particularly preferably 20 ppm or less. When the content ratio of the chlorine component is large, there is a problem that the color tone is deteriorated in the optical material application. On the other hand, in electronic materials, there is a problem that the chlorine component corrodes the metal component in the wiring.

  The glass transition temperature of the cured product of the present invention may be any temperature, and can be controlled to an appropriate temperature according to the purpose, but is generally preferably 100 ° C. or higher, and preferably 120 ° C. or higher. More preferably, it is more preferably 150 ° C. or higher, and particularly preferably 180 ° C. or higher. Below this range, the optical properties may change from the design values under the usage environment, and there is a possibility that the heat resistance necessary for practical use may not be satisfied.

  The refractive index at 589 nm of the cured product of the present invention may be any value, and can be appropriately controlled according to the purpose, but is generally preferably 1.55 or more. Furthermore, it is preferably 1.57 or more, and particularly preferably 1.58 or more. In addition to being thin and light when used in an optical material such as a lens due to its high refractive index, performance such as antireflection can be enhanced by increasing the refractive index difference from the material used together.

The cured product of the present invention preferably has a water absorption of 2% by mass or less after 24 hours at 85 ° C. and 85% humidity. Furthermore, it is preferable that it is 1.5 mass% or less, and it is especially preferable that it is 1 mass% or less. If the water absorption rate is high, the heat and moisture resistance and dimensional stability deteriorate.
The photoelastic coefficient of the cured product of the present invention is preferably 45 × 10 ⁻¹² Pa ⁻¹ or less. More preferably, it is 40 × 10 ⁻¹² Pa ⁻¹ or less, particularly preferably 35 × 10 ⁻¹² Pa ⁻¹ or less, and usually 5 × 10 ⁻¹² Pa ⁻¹ or more. When the photoelastic coefficient is high, the birefringence of the material changes in parts where stress is generated when used for large molded products or when the molded product is bent, which may impair the uniformity of optical properties. There is sex.

[How to make a cured product]
Examples of the method of curing the composition such as the epoxy resin of the present invention with a curing agent include curing by heating and curing by ultraviolet irradiation according to the curing agent.
For example, the epoxy resin of the present invention, a curing agent, and if necessary, a curing accelerator, a phosphorus-containing compound, other resin, an inorganic filler, and a compounding agent are made uniform using an extruder, a kneader, a roll, etc. as necessary. Mix well until the epoxy resin composition of the present invention is obtained, and after potting, melting (without melting if liquid), casting, or molding using a transfer molding machine, etc. The cured product of the present invention can be obtained by heating at 80 to 200 ° C. for 2 to 10 hours.

Moreover, when a photocationic polymerization initiator is included, it can be cured by irradiation with ultraviolet rays. About the ultraviolet irradiation amount, since it changes with resin compositions, it is determined by each curing condition. What is necessary is just the irradiation amount which a resin composition hardens | cures, and should just satisfy | fill the curing conditions with the favorable adhesive strength of hardened | cured material. Since it is necessary for light to pass through in detail at the time of curing, the epoxy resin and the epoxy resin composition of the present invention are desired to have high transparency. Moreover, it is difficult to completely cure these epoxy resins and epoxy resin compositions only by light irradiation, and in applications where heat resistance is required, it is desirable to complete the curing by heating after light irradiation.

Heating after the light irradiation may be performed in a normal curing temperature range of the resin composition. For example, the range of 30 minutes to 7 days at room temperature to 150 ° C. is suitable. Although it changes depending on the composition of the resin composition, the higher the temperature range, the more effective the curing is after light irradiation, and the shorter the heat treatment is. By such heat after-curing, an effect of aging treatment can be obtained.
If necessary, an epoxy resin composition dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylacetamide, N-methylpyrrolidone, or the like as a varnish is added to glass fiber, cap -A prepreg obtained by impregnating a base material such as a bon fiber, a polyester fiber, a polyamide fiber, an alumina fiber, paper, etc. and drying by heating may be hot press molded to obtain a cured product of the resin composition of the present invention. it can. The amount of the solvent used in this case is usually 10% by mass or more, preferably 15% by mass or more, and usually 70% by mass or less in the epoxy resin composition of the present invention. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material containing a carbon fiber can also be obtained as it is by RTM (Resin Transfer Molding) shaping | molding as it is.

<7. Optical material>
The hardened | cured material obtained by hardening | curing compositions, such as an epoxy resin of this invention, can be used for various optical material uses. The optical material refers to general materials used for applications in which light such as visible light, infrared light, ultraviolet light, X-rays, and lasers passes through the material. More specifically, in addition to LED sealing materials such as lamp type and SMD type, the following may be mentioned.

  For example, it is a liquid crystal display device peripheral material such as a substrate material, a light guide plate, a prism sheet, a polarizing plate, a retardation plate, a viewing angle correction film, an adhesive, and a film for liquid crystal such as a polarizer protective film in the liquid crystal display field. In addition, color PDP (plasma display) sealing materials, antireflection films, optical correction films, housing materials, front glass protective films, front glass replacement materials, adhesives, and LED displays that are expected as next-generation flat panel displays LED molding materials, LED sealing materials, front glass protective films, front glass substitute materials, adhesives, and substrate materials for plasma addressed liquid crystal (PALC) displays, light guide plates, prism sheets, deflection plates , Phase difference plate, viewing angle correction film, adhesive, polarizer protective film, front glass protective film in organic EL (electroluminescence) display, front glass substitute material, adhesive, and various in field emission display (FED) Film substrate Front glass protective films, front glass substitute material, an adhesive.

In the optical recording field, VD (video disc), CD / CD-ROM, CD-R / RW, DVD-R / DVD-RAM, MO / MD, PD (phase change disc), hologram memory, optical card disc Substrate materials, pickup lenses, protective films, sealing materials, adhesives, and the like.
In the optical equipment field, they are still camera lens materials, finder prisms, target prisms, finder covers, and light receiving sensor sections. It is also a photographic lens and viewfinder for video cameras. Projection lenses for projection televisions, protective films, sealing materials, adhesives, and the like. These are materials for lenses of optical sensing devices, sealing materials, adhesives, films, and the like. In the field of optical components, they are fiber materials, lenses, waveguides, element sealing materials, adhesives and the like around optical switches in optical communication systems. Optical fiber material, ferrule, sealing material, adhesive, etc. around the optical connector. For optical passive components and optical circuit components, they are lenses, waveguides, LED sealing materials, CCD sealing materials, adhesives, and the like. These are substrate materials, fiber materials, device sealing materials, adhesives, etc. around an optoelectronic integrated circuit (OEIC). In the field of optical fiber, it is an optical fiber for industrial use sensors, displays / signs, etc. for illumination / light guides for decorative displays, and for communication infrastructure and home digital device connection.

<8. Electronic materials>
The hardened | cured material obtained by hardening | curing compositions, such as an epoxy resin of this invention, can be used for various electronic material uses. The electronic material generally indicates materials used around the electronic device such as a semiconductor sealing material, a heat dissipation material, and a laminated plate. Specific examples thereof include the following.
As adhesives for electronic materials, interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films (ACF), Examples thereof include an adhesive for mounting such as anisotropic conductive paste (ACP).

  Examples of the sealing material include capacitor, transistor, diode, light emitting diode, IC, LSI potting, dipping, transfer mold sealing, IC, LSI COB (Chip On Board), COF (Chip On Film). When mounting IC packages for potting sealing for TAB (Tape Automated Bonding), underfill for flip chip, QFP (Quad Flat Package), BGA (Ball Grid Array), CSP (Chip Size Package), etc. Sealing (including reinforcing underfill) and the like.

Examples of semiconductor integrated circuit peripheral materials include resist materials for microlithography for LSI and VLSI materials, thermally conductive materials, heat radiating materials, interlayer insulating layers in multilayer substrates, and the like.
The composition such as an epoxy resin of the present invention can also be applied to an optical semiconductor device. Such an optical semiconductor device can be manufactured by sealing an optical semiconductor element (optical semiconductor chip) with the composition of the epoxy resin of the present invention. As the sealing method, a method of molding (casting and curing) a sealing resin for sealing the optical semiconductor element by a method such as casting, potting or printing can be employed. As molding conditions, molding conditions in sealing molding of a semiconductor element with a curable resin composition that have been conventionally performed can be employed as they are, and may be set as appropriate depending on the composition of the resin composition for optical semiconductor encapsulation.

Next-generation optical / electronic functional organic materials include organic EL element peripheral materials, organic photorefractive elements, optical amplification elements that are light-to-light conversion devices, optical arithmetic elements, substrate materials around organic solar cells, fiber materials, elements Sealing material, adhesive and the like.
Applications other than optical materials and electronic materials include general applications in which an epoxy resin composition is used. For example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulation In addition to materials (including printed circuit boards, wire coatings, etc.), cyanate resin compositions for substrates, additives for other resins, such as acrylate resins as resist curing agents, and the like.

Examples of the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives.
In the field of automobiles and transport equipment, automotive lamp reflectors, bearing retainers, gear parts, anti-corrosion coatings, switch parts, headlamps, engine internal parts, electrical parts, various interior and exterior parts, drive engines, brake oil tanks, automobile protection Rusted steel plates, interior panels, interior materials, protective / bundling wireness, fuel hoses, automobile lamps, glass replacements. In addition, it is a multilayer glass for railway vehicles.

  Further, they are toughness imparting agents for aircraft structural materials, engine peripheral members, protective / bundling wireness, corrosion resistant coatings, and carbon fiber reinforced composite materials. In the construction field, it is interior / processing materials, electrical covers, sheets, glass interlayers, glass substitutes, and solar cell peripheral materials. For agriculture, it is a house covering film.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited by a following example, unless the summary is exceeded. The characteristics of the oligofluorene epoxy resin of the present invention and the oligofluorene having a carbon-carbon double bond of the present invention were evaluated by the following methods. The characteristic evaluation method is not limited to the following method and can be appropriately selected by those skilled in the art.

In addition, the abbreviations and the like of the compounds used in the following examples are as follows.
DMF; N, N-dimethylformamide PET; polyethylene terephthalate

[Method of measuring physical properties of oligofluorene epoxy resin and oligofluorene having a carbon-carbon double bond]
(1) Refractive index measurement of oligofluorene epoxy resin and oligofluorene having carbon-carbon double bond Digital refraction of refractive index at 589 nm of DMF solution of oligofluorene epoxy resin and oligofluorene having carbon-carbon double bond Measurement was performed at a measurement temperature of 20 ° C. using a total RX-7000α (manufactured by Atago Co., Ltd.). The measurement was performed by changing the concentration of the DMF solution, and the oligofluorene epoxy resin and the oligofluorene epoxy resin having a carbon-carbon double bond were assumed to be 1.2. The refractive index of oligofluorene having a carbon-carbon double bond was calculated.

(2) Melting point measurement of oligofluorene epoxy resin and oligofluorene having carbon-carbon double bond Oligofluorene epoxy resin or oligofluorene having carbon-carbon double bond of the present invention is packed in a small amount of capillary, and a melting point measuring device Measurement was performed using SMP3 (manufactured by Stuart Scientific).

(3) Measurement of epoxy equivalent of oligofluorene epoxy resin Measured according to JIS K7236.
(4) Melt Viscosity Measurement of Oligofluorene Epoxy Resin Melt the epoxy resin on a hot plate of a cone plate viscometer (manufactured by Tokai Yagami Co., Ltd.) adjusted to 150 ° C., and measure the viscosity when measured at a rotational speed of 750 rpm. It was measured.

[Method of measuring physical properties of phenoxy resin (high molecular weight epoxy resin)]
(5) Weight average molecular weight and number average molecular weight Using an “HLC-8120GPC apparatus” manufactured by Tosoh Corporation, TSK Standard Polystyrene: F-128 (Mw1,090,000, Mn1) as standard polystyrene under the following measurement conditions , 030,000), F-10 (Mw 106,000, Mn 103,000), F-4 (Mw 43,000, Mn 42,700), F-2 (Mw 17,200, Mn 16,900), A-5000 (Mw 6) , 400, Mn 6,100), A-2500 (Mw 2,800, Mn 2,700), A-300 (Mw 453, Mn 387) using a calibration curve (calibration curve approximation formula: cubic equation), weight The average molecular weight and number average molecular weight were measured as polystyrene conversion values.

Column: “TSKGEL SuperHM-H + H5000 + H4000 + H3000 + H2000” manufactured by Tosoh Corporation
Eluent: Tetrahydrofuran Flow rate: 0.6 ml / min
Detection: UV (wavelength 254 nm)
Temperature: 40 ° C
Sample concentration: 0.1% by mass
Injection volume: 10 μl
(6) Epoxy equivalent Measured according to JIS K 7236 and expressed as a solid content converted value.

(7) Glass transition temperature (Tg)
The polymer epoxy resin or epoxy resin composition solution is applied to a separator (silicone-treated PET film, thickness: 100 μm) with an applicator and dried or cured at 160 ° C. for 1.5 hours and then at 200 ° C. for 1.5 hours. An epoxy resin film having a thickness of about 50 μm was obtained. This film was cut out, and “DSC7020” manufactured by SII Nanotechnology Co., Ltd. was used, and the glass transition temperature was measured by raising the temperature from 30 to 250 ° C. at 10 ° C./min. The glass transition temperature here was measured based on “midpoint glass transition temperature: Tmg” described in JIS K7121 “Plastic Transition Temperature Measurement Method”.

[Method for measuring physical properties of cured oligofluorene epoxy resin]
(8) Measurement of glass transition temperature (Tg) and linear expansion coefficient (α1, α2) The cured product was cut into a cylindrical shape having a thickness of 2 mm and a diameter of 6 mm to obtain a test piece. The analysis was performed using a thermomechanical analyzer (TMA: EXSTAR 6000 manufactured by Seiko Instruments Inc.) in the compression mode using the following measurement method. The glass transition temperature (Tg) and the linear expansion coefficients (α1, α2) in the measurement at the second temperature increase were measured.

(Measuring method)
1st temperature rise: 5 ° C / min, 30 ° C to 250 ° C, 1st temperature drop: 10 ° C / min, 250 ° C to 30 ° C
Second temperature rise: 5 ° C./min, 30 ° C. to 250 ° C. Second temperature drop: 10 ° C./min, 250 ° C. to 30 ° C.
Measuring load 30mN

(9) 1%, 5% thermal weight loss temperature (Td1, Td5)
100 mg of the cured product was scraped, and 10 mg was weighed therefrom to prepare a sample. About this sample, thermal analyzer (TG / DTA: EXSTAR manufactured by Seiko Instruments Inc.)
7200), and the following measurement method was used for analysis. The temperature at the time when the weight of the cured product was reduced by 1% and 5% was measured and defined as a 1%, 5% thermal weight reduction temperature (Td1, Td5).

(Measuring method)
Temperature increase rate: 5 ° C / min, 30 ° C to 600 ° C
Air: Flow rate 200mL / min

(10) Measurement of refractive index and Abbe number The cured product was cut into a rectangular parallelepiped having a length of 40 mm, a width of 8 mm and a thickness of 2 mm to obtain a test piece. The refractive index (D, F, C) and Abbe number were measured with a refractometer (DR-M2 manufactured by ATAGO).

[Synthesis of oligofluorene having a carbon-carbon double bond]
Example 1 Synthesis of bis (9-allylfluoren-9-yl) methane (Compound 2)

To a 100 mL three-necked flask, 10.0 g (29.0 mmol) of bis (fluoren-9-yl) methane (compound 1), 40 mL of DMF, and 8.78 g (72.6 mmol) of allyl bromide were added and cooled with ice. To this was added 9.77 g (87.1 mmol) of tert-butoxypotassium over 10 minutes, followed by aging at room temperature for 5 hours. The reaction mixture was ice-cooled, 15 mL of 3 mol / L hydrochloric acid and 50 mL of water were added, and the slurry was filtered. What was collected by filtration was washed twice with 20 mL of water, and low boiling substances were distilled off by an evaporator. 50 mL of methanol was added to the obtained powder, suspended and washed at 50 ° C., filtered at room temperature, and dried under reduced pressure to obtain a white powder. 10.7 g (yield 87%) of bis (9-allylfluoren-9-yl) methane (compound 2). The ¹ H-NMR chemical shift of Compound 2 is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.04-7.07 (m, 4H), 6.95-6.99 (m, 4H), 6.80-6.82 (m, 8H), 4 .90-4.98 (m, 2H), 4.59-4.71 (m, 4H), 3.08 (s, 2H), 2.50 (d, 4H, J = 7.3 Hz).
m. p. : 97 ° C

[Synthesis of oligofluorene epoxy resin]
Example 2 Synthesis of bis [9- (2,3-epoxypropyl) fluoren-9-yl] methane (Compound 3)

To a 300 mL three-necked flask, 10.5 g (24.8 mmol) of bis (9-allylfluoren-9-yl) methane (Compound 2) and 50 mL of chloroform were added and cooled with water. A solution prepared by dissolving 17.1 g (64.4 mmol) of a 65 wt% m-chloroperbenzoic acid aqueous solution in 120 mL of chloroform was added dropwise over 10 minutes. After aging at room temperature for 5 hours, the reaction solution was left overnight. This was washed with 50 mL of 5 wt% aqueous sodium thiosulfate twice, twice with 50 mL of 1 mol / L aqueous sodium hydroxide solution, and twice with 75 mL of water. The organic layer was dried over anhydrous sodium sulfate and filtered, and then the solvent was distilled off with an evaporator. The residue was dissolved by heating with 15 mL of toluene, 75 mL of methanol was slowly added dropwise at 60 ° C., and then allowed to cool, followed by ice cooling to crystallize the target product, and the first crystal was obtained by filtration. The filtrate was evaporated using an evaporator, and the residue was crystallized in the same manner as the first crystal using 2 mL of toluene and 50 mL of methanol to obtain a second crystal. The first crystal and the second crystal were dried under reduced pressure to obtain a white powder. Bis [9- (2,3-epoxypropyl) fluoren-9-yl] methane (Compound 3) First crystal 6.01 g, second crystal 3.40 g (total yield 83%). The ¹ H-NMR chemical shift and melting point of Compound 3 are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 6.77-7.10 (m, 16H), 3,07-3.24 (m, 2H), 2.29-2.34 (dd, 2H, J = 4.3, 14.1 Hz), 2.05-2.07 (m, 2H), 1.88-1.93 (m, 4H), 1.79-1.84 (m, 2H).
m. p. 137 ° C

  Example 3 Synthesis of bis [9- (2,3-epoxypropyl) fluoren-9-yl] methane (Compound 3)

  In a 100 mL three-necked flask, 10.0 g (23.6 mmol) of bis (9-allylfluoren-9-yl) methane (compound 2), 15 ml of toluene, 6.3 ml of water, N-butyl-N, N-di [2- ( 4-t-butylbenzoyloxy) ethyl] -N-methylammonium monomethyl sulfate 540 mg (1.18 mmol), 8.1% (weight / volume) phosphoric acid aqueous solution 4.29 mL (3.54 mmol), sodium tungstate A hydrate 781 mg (2.36 mmol) was added, and a Dimroth was attached, followed by stirring at 70 ° C. To this, 6.07 ml (70.8 mmol) of 35 wt% hydrogen peroxide was added dropwise over 7 hours, and after further heating for 1 hour, the reaction solution was left overnight and separated to obtain an organic layer.

The organic layers obtained by the above-described method from 4.0 g (9.42 mmol) of bis (9-allylfluoren-9-yl) methane (Compound 2) were combined and washed with 14 ml of 5 wt% aqueous sodium thiosulfate solution. To this, 14 ml of methanol and 1.83 g (13.2 mmol) of potassium carbonate were added and stirred for 1 hour, and then washed successively with 14 ml of 1 mol / L sodium hydroxide aqueous solution and 7 ml of saturated sodium sulfate aqueous solution. The organic layer was dried over anhydrous sodium sulfate and filtered, and then the solvent was partially removed by an evaporator to obtain 26.9 g of a reddish brown oil.

This was heated to 60 ° C., 42 ml of hexane was slowly added dropwise, allowed to cool, then ice-cooled to crystallize the desired product, and a light brown powder was obtained by filtration. The obtained powder was washed with 14 ml of hexane and dried under reduced pressure to obtain 12.1 g of bis [9- (2,3-epoxypropyl) fluoren-9-yl] methane (compound 3) (total yield 81%) I got it.
Comparative Example 1 Synthesis of bis (9-allylfluoren-9-yl) ethane (Compound 4)

Bis (fluoren-9-yl) ethane (5.00 g, 13.9 mmol) and DMF (20 mL) were placed in a 50 mL four-necked flask, purged with nitrogen, and then controlled at 20-30 ° C. with a water bath to control tBuOK (3. When 50 g, 31.2 mmol) was added, the color of the solution changed to a deep red color. Thereafter, a mixed solution of allyl bromide (2.6 ml, 31 mmol) and DMF (2.6 ml) was added dropwise over 30 minutes. During the dropping, when the color of the reaction solution changed from red to light yellow, the dropping was temporarily stopped, and tert-butoxypotassium (2.12 g, 27.8 mmol) was added in two portions. After stirring for 30 minutes at an internal temperature of 25 ° C., the completion of the reaction was confirmed by HPLC. Distilled water (20 mL) was added and filtered, and the residue was dispersed in methanol (15 mL) and the resulting slurry solution was refluxed. The slurry solution was filtered and subjected to suction filtration, and then dried under reduced pressure at 80 ° C. until a constant weight was obtained, whereby 4.76 g (yield 78%, 97% after HPLC pure) of Compound 4 was obtained as a white solid. The ¹ H-NMR chemical shift of Compound 4 is shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.73-7.72 (m, 4H), 7.39-7.36 (m, 4H), 7.30-7.26 (m, 4H), 7 .03-7.01 (m, 4H) 4.92-4.83 (m, 2H), 4.53-4.48 (m, 4H), 2.31 (d, 4H, J = 3.4 Hz) ), 1.27 (s, 4H).
m. p. 176 ° C

  Comparative Example 2 Synthesis of bis [9- (2,3-epoxypropyl) fluoren-9-yl] ethane (Compound 5)

Compound 4 (0.997 g, 2.27 mmol) was placed in a 50 mL three-necked flask and dissolved by adding chloroform (9.1 mL). A solution prepared by dissolving a 65 wt% m-chloroperbenzoic acid aqueous solution (1.453 g, 5.89 mmol) in chloroform (7.5 mL) is added dropwise over 1 hour, and the mixture is stirred at 25 ° C. for 6 hours. After confirming the completion of the reaction by HPLC, washing is performed using a 5 wt% aqueous sodium thiosulfate solution (5 ml × 3 times) and a 1 mol / L aqueous sodium hydroxide solution (5 mL). After adding 0.2 mL of tributyl phosphite and stirring for 30 minutes, it was washed with a 1 mol / L aqueous sodium hydroxide solution (5 mL) and demineralized water (5 mL). Magnesium sulfate was added to the organic layer, dried and filtered, and then the organic layer was concentrated under reduced pressure. Methanol (5 mL) was added for crystallization, and suction filtration was performed. The residue was washed with methanol (15 mL) and dried to a constant weight at 80 ° C. to obtain 0.826 g (yield 77%, HPLC purity 97%) of compound 5 as a white solid. The ¹ H-NMR chemical shift and melting point of Compound 5 are shown below.

¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.77-7.74 (m, 4H), 7.42-7.37 (m, 4H), 7.33-7.29 (m, 4H), 7 .10-6.99 (m, 4H) 2.10-2.08 (m, 2H), 2.02-1.96 (m, 4H), 1.85-1.83 (m, 2H), 1.66-1.60 (m, 2H), 1.29 (s, 4H).
m. p. : 228 ° C
Table 1 shows measured values of the refractive index of the DMF solution of Compound 3 and Table 2 shows measured values of the refractive index of the DMF solution of Compound 5. Table 3 also shows the refractive index values and melting point values of Compound 3 and Compound 5 obtained by extrapolation.

  From Table 3, when comparing the refractive index of the compound 3 of Example 2 and the compound 5 of Comparative Example 2, it can be seen that the refractive index is 1.65, both of which are high. On the other hand, the compound 3 of Example 2 which is the oligofluorene epoxy resin of the present invention has a lower melting point than the compound 5 of Comparative Example 2, and thus is considered to be excellent in workability. Usually, it is considered that the shorter the alkylene group of the crosslinking group, the higher the melting point. However, the oligofluorene epoxy resin of the present invention has a high refractive index and a low melting point by making the crosslinking group a methylene group. There is a tendency to have unique characteristics.

From the above, it is considered that the oligofluorene epoxy resin of the present invention has a high refractive index, a low melting point and excellent workability.
Table 4 shows the measured values of the refractive index of the DMF solution of Compound 2, and Table 5 shows the measured values of the refractive index of the DMF solution of Compound 4. Table 6 also shows the refractive index values and melting point values of Compound 2 and Compound 4 obtained by extrapolation.

  From Table 6, it can be seen that when the refractive index of Compound 2 of Example 1 and that of Compound 4 of Comparative Example 1 are compared, the refractive indexes are both 1.66 and high values. On the other hand, since the compound 2 of Example 1 which is an oligofluorene having a carbon-carbon double bond of the present invention has a lower melting point than the compound 4 of Comparative Example 1, it is considered that the processability is excellent. . Usually, it is considered that the shorter the alkylene group of the cross-linking group, the higher the melting point. However, the oligofluorene having a carbon-carbon double bond of the present invention also has a methylene group as in the case of the oligofluorene epoxy resin of the present invention. Therefore, it tends to have a unique characteristic of having a low melting point while having a high refractive index.

From the above, the oligofluorene having a carbon-carbon double bond of the present invention is not only a useful raw material for the oligofluorene epoxy resin of the present invention, but is itself useful as a curable resin composition.
(Example 4)
[Production and evaluation of phenoxy resin (high molecular weight epoxy resin)]
35.0 g of the compound 3 (epoxy equivalent 230) obtained by the method of Example 3 as a bifunctional epoxy resin, and 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol (hydroxyl equivalent) as a bisphenol compound 155, manufactured by Honshu Chemical Industry Co., Ltd.) 23.1 g, 0.32 g of a 27 mass% tetramethylammonium hydroxide aqueous solution as a catalyst, and 31.3 g of cyclohexanone as a reaction solvent were placed in a reaction vessel equipped with a stirrer, and nitrogen gas The reaction was performed at 145 ° C. for 8 hours in an atmosphere. Thereafter, methyl ethyl ketone was added as a solvent for dilution to adjust the solid content concentration to 50% by mass. The obtained phenoxy resin (high molecular weight epoxy resin) had an epoxy equivalent of 3,000 g / equivalent and a weight average molecular weight of 4,800. Moreover, it was 139 degreeC when the solvent was removed by the above-mentioned method and the glass transition temperature was measured.

(Example 5)
Phenoxy resin (high molecular weight epoxy resin) obtained in Example 4 and bisphenol A novolac type polyfunctional epoxy resin 80% by mass MEK solution (trade name “157S65B80” manufactured by Mitsubishi Chemical Corporation) ”and 2 as a curing agent A 20 mass% MEK solution of ethyl-4 (5) -methylimidazole (trade name “EMI24” manufactured by Mitsubishi Chemical Corporation) was weighed out so that the mass ratio of the solid content was 95: 5: 0.5. The epoxy resin composition was obtained by stirring well.
About the obtained epoxy resin composition, when the cured film was produced by the above-mentioned method and the glass transition point was measured, it was 158 degreeC.

(Example 6)
[Production and evaluation of cured oligofluorene epoxy resin]
Epoxy resin (Compound 3 or PG100: manufactured by Osaka Gas Chemical Co., Ltd.) and acid anhydride (MH700: manufactured by Shin Nippon Rika Co., Ltd.) were blended in the ratios shown in Table 7, heated to 80 ° C. and stirred until uniform. Then, it cooled to 60 degreeC, the catalyst (PX-4MP: Nippon Chemical Industry Co., Ltd.) was added, it stirred until it became uniform, and the composition liquid was created.

  Create two glass plates with a release PET film inside and adjust the thickness to 2 mm to create a casting plate. The composition liquid was cast on a casting plate, heated at 100 ° C. for 3 hours, and further heated at 130 ° C. for 3 hours to obtain a cured product.

  From Table 7, it can be seen that Compound 3 has a lower melt viscosity of the epoxy resin than PG100 and is excellent in workability. Further, the cured product of Compound 3 has a refractive index as high as that of a cured product of PG100, which is a known high-refractive epoxy resin. Td1, Td5) is higher than the cured product of PG100, and is considered to have high thermal stability.

  Example 7 Synthesis of Epoxy Acrylate (Compound 6)

Compound 3 (0.400 g, 876 μmol), tetramethylammonium chloride (2.0 mg, 18 μmol), 3,5-di-tert-butyl-4-hydroxytoluene (2.0 mg, 9.1 μmol), into a 50 mL three-necked flask, Acrylic acid (690 μL, 10.1 mmol) was added and stirred at 120 ° C. for 3 hours. After confirming the end of the reaction by NMR,
The reaction solution was cooled to room temperature, and 2 ml of ethyl acetate was added. The organic layer was washed twice with 2 ml of saturated aqueous sodium sulfate solution and twice with 2 ml of saturated aqueous sodium hydrogen carbonate solution, and then the solvent was distilled off to obtain 0.527 g of compound 6 as a tan viscous liquid (yield 100%, NMR purity 96%).

Claims (11)

An oligofluorene epoxy resin represented by the following general formula (1).

(Wherein R ¹ and R ² are each independently a direct bond or an optionally substituted carbon atom having 1 to 1 carbon atoms.
An alkylene group of 0, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10
An acyloxy group, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.
R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. ) The oligofluorene epoxy resin according to claim ^1, wherein R ¹ and R ² are methylene groups. The oligofluorene having a carbon-carbon double bond represented by the following general formula (2) is oxidized to obtain an oligofluorene epoxy resin represented by the general formula (1) according to claim 1 or 2. And a method for producing an oligofluorene epoxy resin.

(Wherein R ¹ and R ² are each independently a direct bond or an optionally substituted carbon atom having 1 to 1 carbon atoms.
An alkylene group of 0, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10
An acyloxy group, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.
R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. ) An oligofluorene epoxy resin composition comprising the oligofluorene epoxy resin according to claim 1 or 2. An oligofluorene compound having a carbon-carbon double bond, which is represented by the following general formula (2):

(Wherein R ¹ and R ² are each independently a direct bond or an optionally substituted carbon atom having 1 to 1 carbon atoms.
An alkylene group of 0, an optionally substituted arylene group having 4 to 10 carbon atoms, or an optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or, it is selected from the group consisting of an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms. Two or more groups are linked by an oxygen atom, an optionally substituted sulfur atom, an optionally substituted nitrogen atom or a carbonyl group,
R ^{4 to} R ⁹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 10 carbon atoms, an optionally substituted aryl group having 4 to 10 carbon atoms, or optionally substituted. C1-C10 acyl group, C1-C10 alkoxy group which may be substituted, C1-C10 aryloxy group which may be substituted, C1-C1 which may be substituted 10
An acyloxy group, an optionally substituted amino group, a sulfur atom having a substituent, a halogen atom, a nitro group, or a cyano group. However, at least two groups adjacent to each other among R ^{4 to} R ⁹ may be bonded to each other to form a ring.
R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
n shows the integer value of 1-5. ) An epoxy (meth) acrylate compound represented by the following general formula (5):

( Wherein R ¹ and R ² are each independently a direct bond or an optionally substituted carbon atom having 1 to 1 carbon atoms.
0 alkylene group, optionally substituted arylene group having 4 to 10 carbon atoms, or substitution
An optionally substituted aralkylene group having 5 to 12 carbon atoms,
Or an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted carbon
Is it an arylene group having 4 to 10 carbon atoms and an optionally substituted aralkylene group having 5 to 12 carbon atoms?
Two or more groups selected from the group consisting of an oxygen atom, an optionally substituted sulfur atom, and a substituent
A group connected by a nitrogen atom or a carbonyl group, which may be
R ^{4 to} R ⁹ are each independently a hydrogen atom or an optionally substituted alkyl having 1 to 10 carbon atoms.
Kill group, optionally substituted aryl group having 4 to 10 carbon atoms, optionally substituted carbon
An acyl group having 1 to 10 carbon atoms, an optionally substituted alkoxy group having 1 to 10 carbon atoms,
C1-C10 aryloxy group which may be substituted, C1-C10 which may be substituted
Acyloxy group, optionally substituted amino group, sulfur atom having a substituent, halogen
An atom, a nitro group, or a cyano group. However, at least two adjacent R ^{4 to} R ⁹
These groups may be bonded to each other to form a ring.
R ¹⁰ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 10 carbon atoms.
R ¹² is a hydrogen atom or a methyl group,
R ¹³ represents a hydrogen atom or an acyl group.
n shows the integer value of 1-5. ) A composition comprising the oligofluorene compound having a carbon-carbon double bond according to claim 5 or the epoxy (meth) acrylate compound according to claim 6. A cured product obtained by curing the oligofluorene epoxy resin composition according to claim 4 or the composition according to claim 7. The cured product according to claim 8, wherein the halogen atom content is 1000 ppm by mass or less.   An optical material comprising the cured product according to claim 8 or 9.   An electronic material comprising the cured product according to claim 8 or 9.